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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
" %
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)
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
Surroundings
The surroundings is the universe apart from the system. This is where we mostly do our measurements. Open system Closed system Isolated system
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
Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14
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
(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).
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
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
(12)
(C 2)
NO(g) N2 O4 (l)
N2 O4 (l)
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
Second law
The entropy, S , of an isolated system tends to increase.
Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14
(14)
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
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 )
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)
(25)
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 .
water
(C 3)
Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10
steam
(C 4)
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.
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
Irreversible change
Stot = Ssystem + Ssurrounding > 0 To caculate S we need to nd a reversible pathway. (28)
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
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
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
(29)
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 )
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. .
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
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)
Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6
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
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)
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
(44)
Phase diagram
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14
Reading
Chapter 4 Thermodynamics: the Second Law Chapter 5 Physical equilibria: pure substances
Phase
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
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
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
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.
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.
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)
Note: The molar volume of liquids and solids does change very little with pressure. However, the molar volume of gases strongly depends on pressure.
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
p p
Lecture 13 & 14
dp
T
(55)
= Sm
p
and
= Vm
T
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
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)
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)
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
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
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
F : Number of degrees of freedom e.g. pressure, temperature, mole fraction C : Number of components P : Number of phases
CO2
He