11 tayangan

Diunggah oleh Mohamed Abdulla

a

- Lecture 2 Analysis of Degrees of Freedom
- Phys 253 Thermal Physics
- J2006_Termodinamik
- s2_s2_syllabus_btech_2013_scheme
- PNAS-1960-Craig-the thermodynamics of sea water.pdf
- Thermo.pdf
- physical metallurgy
- PPE 801.2_Hydraulic Analysis &DAP.
- Thermodynamics unit 1 Notes
- CCD Revisited-An Essential Element of a MI and RBI Program Secured
- Solvent Extraction
- Lecture Notes _ Thermodynamics
- SC RE Chap4- Phase Behaviour
- 1.3.3.a.ak Thermodynamics 1
- Presipitation Hardening
- PETSOC-09-07-18 Gas Condensate reservoir performance.pdf
- CM1502 Tutorial 5 Solutions
- PIPE CNS 04
- Fundamentals of Energy Conversion
- prigogine1989.pdf

Anda di halaman 1dari 32

Dr N Hendrik Nahler

email: n.nahler@hw.ac.uk oce: G.30

2012/13

Introduction

About me

2012: Royal Society University Research Fellow, Heriot-Watt University 2007 2012: RS-URF, Durham University 2005 2007: Alexander von Humboldt Fellowship, UCSB 2003 2005: EU Marie Curie Fellowship, Bristol 2002: PhD in Molecular Physics, MPI for Fluid Dynamics, G ottingen

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

About my research

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

Thermodynamics

Where does it t in the big scheme?

Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes.

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

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

Example

Thermodynamics Reaction Kinetics diamond graphite

" %

Thermodynamics all about if

If a reaction can occur. Applicable if a system is in stable or metastable equilibrium. If the driving force is sucient to enforce a favourable transformation.

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

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.

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

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

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

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

Reading list

Textbook for this course

2 3 Thermodynamics

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

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

4 5 6 7 8

Additional reading

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

Thermodynamics N H Nahler

Key concepts

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

Laws of thermodynamics

1

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

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

Reading

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

System

The system is what we are interested in. Examples: reaction components, engine, biological cell.

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

Surroundings

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

Thermodynamics

First law

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

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

Alternative denition

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

Classical mechanics

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

Internal Energy, U

The internal energy is made up of kinetic energy, rotational energy, vibrational energy, potential energy etc.

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

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

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

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

Expansion

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

Compression

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

Lecture 13 & 14

CuCO3 (s) + 2 HCl(aq)

solid liquid

liquid liquid gas

(C 1)

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

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

Enthalpy, H

If our chemistry happens in an open system then energy put into the system will be partly given back to surroundings. Therefore we dene a new quantity that avoids the complication of work of expansion by the system on the surroundings:

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

Denition of Enthalpy, H

H = U + pV (7)

Change in enthalpy

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

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

Thermodynamics N H Nahler

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

dU = U T

CV

dT +

V

U V

Lecture 5 & 6

dV (10)

T

dH =

H T

Cp

dT +

p

H p

dp (11)

T

Calculate the change in internal energy, U , when 1 mol of zinc is dissolved in aqueous hydrochloric acid at 298 K and atmospheric pressure given that the heat that is liberated is 151 000 J. How big is the change in enthalpy, H ?

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

Thermochemistry

Change of enthalpy in chemical reactions

exothermic process endothermic process releases heat absorbs heat H < 0 H > 0

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

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

(12)

2 NO(g) + O2 (g) given

1 2 N2 (g) 1 +2 O2 (g)

(C 2)

NO(g) N2 O4 (l)

N2 O4 (l)

Thermodynamics

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

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

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

Thermodynamics N H Nahler

Second law

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

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

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

(14)

Thermodynamics

nal

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

dS = S =

dS =

initial

Clausius inequality

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

Lecture 13 & 14

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

Lecture 13 & 14

Example

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

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)

(23)

Examples

1

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

Addition of heat evaporates water. Removal of heat freezes water. Melting at melting temperature, Tf : fus H (Tf ) fus S = Tf Vaporization at the boiling temperature, Tb : vap H (Tb ) vap S = Tb (24)

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

(25)

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

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

Examples

1 Thermodynamics N H Nahler Lecture 1 & 2

273 K, 1 bar

water

(C 3)

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

2

373 K, 1 bar

steam

(C 4)

3

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

Thermodynamics

Key concepts

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

Laws of thermodynamics

1

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

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

Reading

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

Reversible change

Stot = Ssystem + Ssurrounding = 0 (27)

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

Irreversible change

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

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

Lecture 13 & 14

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

1 2 3 4

Construct reversible thermodynamic cycle Calculate entropy changes of individual changes. Calculate the entropy change of the system. Calculate the entropy change of the surroundings and the total entropy change (Stot > 0).

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

Phase changes

solids liquids gases relatively ordered some order disordered low entropy medium entropy high entropy

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

Changes in molecules

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

Examples

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

Lecture 13 & 14

How can we calculate the entropy change of a mixture of ideal gases? Is there actually a change in entropy? Ideal gases do not interact.

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

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

(29)

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

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

0.6

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

mixS / nR

0.4

0.2

0 0 0.5 1

Mole fraction of A, xA

mix S = nA R ln

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

Thermodynamics

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

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

Mixing functions

Macroscopic thermodynamics

A (l) B (l)

Thermodynamics N H Nahler Lecture 1 & 2

Lecture 3 & 4

mix S = nR (xA ln xA + xB ln xB )

A (l) + B (l)

Molecular thermodynamics

B A B B A A A

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

A A A B

A B

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

What is the number of ways of placing NA molecules A into a cubic lattice with a total of N sites?

Note that NA = Avogadros number in this context. We express Avogrados number as NAvo. .

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

Counting possibilities

Lets say we have NA Jills and N oces

Number of ways of placing . . . . . . rst Jill = N . . . second Jill = N 1 . . . third Jill = N 2 ... . . . the NA th Jill = N (NA 1) = N NA + 1

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

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

Counting possibilities

Now we have overcounted the possibilities W

Several dierent ways lead to the same microstate. For example, in the case of:

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

# # # # # #

1 1 2 2 3 3

# # # # # #

2 3 1 3 1 2

# # # # # #

3 2 3 1 2 1

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

Counting possibilities

Thermodynamics N H Nahler

To account for this overcounting, how many ways of placing molecules on a given set of sites?

1 2 3 . . . NA molecules of A molecules of A molecules of A molecules of A molecules of A 1 2 6 . . . identical congurations identical congurations identical congurations identical congurations identical congurations (35)

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

NA !

W =

N! (N NA )!NA !

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

Counting possibilities

Thermodynamics

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

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

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

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

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

Stirlings approximation

The factorials are inconvenient for calculations. Fortunately . . . ln N ! N ln N N This approximation becomes more exact for large N . We typically deal with N of the order of 1023 .

Stirling's approximation

1 1,000 Y = ln N! Y = N ln N - N 10 100 1,000

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

100

100

10

10

0.1 1 10 N 100

0.1

Entropy of mixing

Making use of the Stirling approximation

S = kB ln W = kB ln N! (N NA )!NA ! (37) (38) (39) + NA ln N NA N NA (40)

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

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

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

Thermodynamics N H Nahler

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

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

Third law

A perfect crystal at T = 0 K has zero entropy.

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

Alternative denitions

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

Residual entropy

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

Thermodynamics N H Nahler

CO

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

H2 O

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

What do we know so far about entropy and the direction of change?

isolated system non-isolated system dSsystem > 0 dSsystem + dSsurroundings > 0 spontaneous spontaneous

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4

Clausius inequality

dS dq T (system) (43)

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

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

Implications of entropy

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

Example

Thermodynamics

2 H2 (g) + O2 (g)

H2 O(l)

(C 7)

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

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

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

(44)

Key concepts

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

Phase diagram

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

Reading

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

Thermodynamics N H Nahler

Phase

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

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

Constituent

A constituent is a chemical species (ion or molecule) that is present in the system.

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4

Component

A component is a chemically independent constituent of a system where C = . . . is the number of components in the system.

water NaCl solution NaCl iron oxide "rust" iron

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

ice

P=2 C =1

P=2 C =2

P=1 C =2

From the Clausius inequality: dQ dS and T T dS dH T dS dH 0 dH T dS 0 (45)

Thermodynamics N H Nahler

dH = dQ

(p = const.)

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

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

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

We describe changes in an open systems where the pressure is constant with the Gibbs free energy.

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

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

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

Constant temperature and volume

Thermodynamics

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

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

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

Maximum work

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

The (molar) Gibbs free energy varies with pressure. In general: Gm = Gm (pf ) Gm (pi ) withp = pf pi Gm = Vm p T = const. (52)

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

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

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

The (molar) Gibbs free energy varies with temperature: Gm = Gm (Tf ) Gm (Ti ) withT = Tf Ti Gm = Sm T p = const. (54)

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

Thermodynamics

dG = G T G T dT +

p

G p

Lecture 3 & 4

dp

T

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

= S

p

and

G p

=V

T

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

p

p p

Lecture 13 & 14

dp

T

(55)

= Sm

p

and

= Vm

T

Thermodynamics

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

p

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

Thermodynamics N H Nahler

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

chemical potential,

Lecture 1 & 2

= Vm

T

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

Phase boundaries

Thermodynamics N H Nahler

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

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

Lecture 13 & 14

dp trs S = dT trs V

Clapeyron equation

(56)

Thermodynamics N H Nahler

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

p p

(57)

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

dp =

Lecture 13 & 14

(58) (59)

The entropy of vaporization at temperature T is equal to vap H /T . dp vap H = dT T vap V Slope of solid-liquid boundary (60)

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6

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

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

Clausius-Clapeyron

Thermodynamics

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

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

Temperature increase

gas

gas

supercritical fluid

liquid

liquid

Thermodynamics

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

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

Triple point

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

Liquid phase

Limitations

For a substance with a volume increase from solid to liquid (most substances but not water), the liquid phase does only exist above the triple point temperature Tt and below the critical temperature Tc . For any substance the liquid phase does not exist below the triple point pressure pt .

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

Phase rule

F =C P +2 (65)

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

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

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

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

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

CO2

He

- Lecture 2 Analysis of Degrees of FreedomDiunggah olehAhmed Ali
- Phys 253 Thermal PhysicsDiunggah olehdavid_berardo6537
- J2006_TermodinamikDiunggah olehVinot Nathan
- s2_s2_syllabus_btech_2013_schemeDiunggah olehsaniljayamohan
- PNAS-1960-Craig-the thermodynamics of sea water.pdfDiunggah olehhumejias
- Thermo.pdfDiunggah olehbansallove2008
- physical metallurgyDiunggah olehapurv salunke
- PPE 801.2_Hydraulic Analysis &DAP.Diunggah olehEhigiator Joseph
- Thermodynamics unit 1 NotesDiunggah olehkapilraj_mech
- CCD Revisited-An Essential Element of a MI and RBI Program SecuredDiunggah olehSaif Eldin
- Solvent ExtractionDiunggah olehaaa
- Lecture Notes _ ThermodynamicsDiunggah olehAnonymous qeSCvmyf
- SC RE Chap4- Phase BehaviourDiunggah olehweldsv
- 1.3.3.a.ak Thermodynamics 1Diunggah olehLary Bags
- Presipitation HardeningDiunggah olehVendi Supendi
- PETSOC-09-07-18 Gas Condensate reservoir performance.pdfDiunggah olehEduardo Ustarez
- CM1502 Tutorial 5 SolutionsDiunggah olehJim Hippie
- PIPE CNS 04Diunggah olehrobert carbungco
- Fundamentals of Energy ConversionDiunggah olehJohn
- prigogine1989.pdfDiunggah olehJuan Pablo Ramirez Monsalve
- 04 Thermodynamics.pdfDiunggah olehrestika
- Engineering Thermodynamics_Print Version - Wiki Books, Collection of Open-content TextbooksDiunggah olehNishant Chugh
- Thermal EquilibriumDiunggah olehHarsh Walia
- objectives.docxDiunggah olehEunielyn Secreto
- Chap 1 ProbsDiunggah olehhawxfly
- phase diagramsDiunggah olehapi-213793181
- ME 201 BasicsDiunggah olehmz_haq
- TF9 ReportDiunggah olehTing Kee Chuong
- thermodynamicsDiunggah olehMacks
- Icy DrinksDiunggah olehMubaraq Rasala

- CompressorDiunggah olehshinejbh
- LiDiunggah olehMohamed Abdulla
- Topic-2.3Diunggah olehMohamed Abdulla
- Legalisation Application Form PRINTABLEDiunggah olehMohamed Abdulla
- ac.els-cdn.com_S0032591002002061_1-s2.0-S0032591002002061-mainDiunggah olehMohamed Abdulla
- ac.els-cdn.com_S0032591002001961_1-s2.0-S0032591002001961-mainDiunggah olehMohamed Abdulla
- AttritionDiunggah olehMohamed Abdulla
- GF-CES-65-10Diunggah olehMohamed Abdulla
- NucleationDiunggah olehMohamed Abdulla
- Nozzel DistribeeDiunggah olehMohamed Abdulla
- C18OP_ Assignment__2013-14(1)Diunggah olehMohamed Abdulla
- SweDiunggah olehMohamed Abdulla
- Finllay AppendixDiunggah olehMohamed Abdulla
- 299 - tbcDiunggah olehMohamed Abdulla
- Using a New Life Cycle Assessment a Range Different Nitrogen Concentration Fertilizers Was Analyzed Using a Basis of One Ton of Winter Wheat in Rothamsted EnglandDiunggah olehMohamed Abdulla
- Minutes From 12th FebruaryDiunggah olehMohamed Abdulla
- ButaneDiunggah olehRatu Fajrina Hanifa
- 1Diunggah olehMohamed Abdulla
- Control Engineering Exam 2011-2012 7 No AnswersDiunggah olehMohamed Abdulla
- Peer Review FormDiunggah olehMohamed Abdulla
- Meeting 14Diunggah olehMohamed Abdulla
- WhatDiunggah olehMohamed Abdulla
- Pr 0 Int 0.2Diunggah olehMohamed Abdulla
- Pressure Measurement by ManometerDiunggah olehMohamed Abdulla
- Recycling of Waste Tyre Rubber Into Oil AbsorbentDiunggah olehMohamed Abdulla

- Mid Term Assessment HOS60303 082014Diunggah olehDevendren Sathasivam
- Fundamentals Of Gas Laws.pdfDiunggah olehMalouk Cheniouni
- BoilerDiunggah olehAdrian Castillo
- Thermal Modeling for Building Integrating Ventilated PV FacadeDiunggah olehsaqi3633
- FIN EFFICIENCYDiunggah olehDigonto Chowdhury
- TemucoDiunggah olehAnonymous eJCLQ6
- Chemical EquilibriumDiunggah olehMarilag Sadicon
- hw09Diunggah olehJeriesPhilipAbedrabbo
- Status of Airconditioners in AustraliaDiunggah olehMasir Amadzai
- SQ Series Manual (2-316.21)Diunggah olehOdunlami
- Mass Transfer Flashcards - CramDiunggah olehrex tanong
- Ind Eng Che Fun15, 59.pdfDiunggah olehIngrith Mar
- p06Diunggah olehAnonymous I13s99
- Steam-Best-Practices-Report.pdfDiunggah olehAtif Ahmad Khan
- Standard Mesahill Rental RateDiunggah oleharenestar
- Ashrae2011 HpDiunggah olehthrandos
- 03.BoltzGibbsShannonDiunggah olehroxy8marie8chan
- Chap 3 ThermodynamicsDiunggah olehAsmawi Mohd Khailani
- VT96Diunggah olehJuan Dela Cruz
- A Robust Numerical Model for Characterizing the SyngasDiunggah olehSamuelogico Samuel
- Case Study Batch Reaction Lesson 1Diunggah olehHamdan Yusoff
- InTech-Solar Energy Drying SystemsDiunggah olehAbas S. Acmad
- Heat Rejection in Condensers Desuperheating, Condensation in SuperheatedDiunggah olehyamakun
- Properties of Pure SubstanceDiunggah olehAbid Sufian Husin
- Morini Lorenzo Tesis Thermal Management PhevDiunggah olehSantiago Molina
- CY11001_PKCDiunggah olehAyush Kumar
- Rankine ReheatDiunggah olehManik Singh
- ENERGY AND EXERGY ANALYSIS OF A GEOTHERMAL POWER STATION WITH TWO-PHASE CLOSED THERMOSYPHON SYSTEM IN AN ORGANIC RANKINE CYCLEDiunggah olehIJAET Journal
- 50ejq Ewq UsDiunggah olehBianel Peralta
- R1 Complete AllDiunggah olehwandee2393