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Recommended Books
1. Smith J.M., Van Ness H.C., Abbott M.M., Chemical Engineering Thermodynamics, 6th Ed. McGraw-Hill International Edition. 2. J.R. Elliott, and Carl T. Lira, Introductory Chemical Engineering Thermodynamics, Prentice Hall, (1999). 3. T.D. Eastop, A. McConkey, Applied Thermodynamics for Engineering Technologists 5th Ed. Published by Educational Low Price Books Scheme.
ASSESSMENT PLAN
ACTIVITY PROBLEM SHEET 1 MID TERM EXAM PROBLEM SHEET 2 END TERM EXAM WEEK ISSUE: W6 SUBMIT: W8 W9 ISSUE : W13 SUBMIT: W15 W17 MARKS 10 35 15 40
GRADING CRITERIA
ASSIGNMENTS
COMPLETENESS NEATNESS PRESENTATION ON-TIME APPROACH ACCURACY NEATNESS COMPLETENESS READABILITY
EXAMINATIONS
Course Outline
http://pu.edu.pk/program/show/2501/B.Sc.-Engineering.html Fundamental Concepts
Basic Definitions in thermodynamics Laws of thermodynamics Volumetric properties- Equations of state Property relations for pure substances
Concept of Fugacity Concept of Exergy Fluid flow processes Power generation (Internal Combustion Engines, Gas Turbines, and Steam power Plant) Refrigeration,Air conditioning and water cooling Liquefaction of gases
1- Basic Definitions
Thermodynamics System and Surroundings Heat and Work Intensive properties Extensive properties State function and Path function Temperature Pressure Volume Internal Energy Enthalpy Entropy Helmholts Energy Gibbs Free Energy
What is Thermo?
ENERGY Science Energy Conversion What is Energy? Cause Changes - Work, Heat, etc. Energy is property of matter! Therefore, ENERGY and PROPERTY interrelations
Thermo Vocabulary
System, Surroundings, and Boundary Closed System - Control Mass Open System - Control Volume Control Surface Adiabatic System - NO Heat Transfer Isolated System - NO Energy Transfer
Forms of Energy
TOTAL Energy
thermal, kinetic, potential, electric, magnetic, nuclear, .
Macroscopic vs. Microscopic INTERNAL Energy (U) - sum of ALL microscopic energies
System PROPERTIES
Extensive
m, V, U, E
Intensive
T, P, , u, e
Pressure Scales
Gauge pressure Local atm. pressure Standard atm. pressure Vacuum pressure
Absolute pressure
Temperature Measurement
Temperature: measure of hotness or coldness indicating the direction in which heat (energy) will spontaneously flow, i.e., from a hotter body (one
at a higher temperature) to a colder one (one at a lower temperature).
Temperature Standards
Temperature scale (ITS-90) Definition of the degree
Kelvin K, defined as the 1/273.16 fraction of the thermodynamic temperature of the triple point of water (TPW).
Thermo Laws
0th Law: TA=TC and TB=TC then TA=TB 1ST Law - Energy Conservation 2ND Law - Process Direction 3RD LAW pure crystalline substance at 0K has 0 entropy.
In Conclusion
Be imaginative Try to differentiate Make sense of what you study Work and think hard and smart Thermodynamics is a science of ENERGY and MATTER and their relations
Laws of Thermodynamics
Laws of Thermodynamics
1st Law of thermodynamics
Definition Mathematical formulation Applications
Concepts of Equilibrium
Equilibrium Mathematical formulation Applications
Phase equilibrium Reaction equilibrium
Thermodynamics
Changes in a system are associated with the transfer of energy Natural systems tend toward states of minimum energy
Energy States
Unstable: falling or rolling Stable: at rest in lowest energy state Metastable: in low-energy perch
Figure 1.1. Stability states. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Thermodynamics
a Phase: a mechanically separable portion of a
system
Mineral Liquid Vapor a Reaction: some change in the nature or types of phases
in a system reactions are written in the form: reactants = products
Thermodynamics
The change in some property, such as G for a reaction of the type: 2A + 3B =C +4D G = (n G)products - (n G)reactants = GC + 4GD - 2GA - 3GB
Thermodynamics
For a phase we can determine V, T, P, etc., but not G or H We can only determine changes in G or H as we change some other parameters of the system
Example: measure H for a reaction by calorimetry - the heat given off or absorbed as a reaction proceeds
Arbitrary reference state and assign an equally arbitrary value of H to it: Choose 298.15 K and 0.1 MPa (lab conditions) ...and assign H = 0 for pure elements (in their natural state - gas, liquid, solid) at that reference
Thermodynamics
In our calorimeter we can then determine H for the reaction:
H = -910,648 J/mol
= molar enthalpy of formation of quartz (at 298, 0.1) It serves quite well for a standard value of H for the phase Entropy has a more universal reference state: entropy of every substance = 0 at 0K, so we use that (and adjust for temperature)
Thermodynamics
For other temperatures and pressures we can use the equation:
dG = VdP SdT
GT
P2
GT
1 P1
z
P2 P1
VdP
z
T2 T1
SdT
Thermodynamics
If V and S are constants, our equation reduces to:
Thermodynamics
In Worked Example 1 we used
Agreement is quite good (< 2% for change of 500o and 500 MPa or 17 km)
Thermodynamics
Summary thus far:
G is a measure of relative chemical stability for a phase We can determine G for any phase by measuring H and S for the reaction creating the phase from the elements We can then determine G at any T and P mathematically Most accurate if know how V and S vary with P and T dV/dP is the coefficient of isothermal compressibility dq/dT is the heat capacity (Cp) Use? If we know G for various phases, we can determine which is most stable Why is melt more stable than solids at high T? Is diamond or graphite stable at 150 km depth? What will be the effect of increased P on melting?
Does the liquid or solid have the larger volume? High pressure favors low volume, so which phase should be stable at high P?
Figure 1.2. Schematic P-T phase diagram of a melting reaction. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
Does liquid or solid have a higher entropy? High temperature favors randomness, so which phase should be stable at higher T?
We can thus predict that the slope of solid-liquid equilibrium should be positive and that increased pressure raises the melting point.
The phase assemblage with the lowest G under a specific set of conditions is the most stable
Would the slope for the liquid be steeper or shallower than that for the solid?
Figure 1.3. Relationship between Gibbs free energy and temperature for the solid and liquid forms of a substance at constant pressure. Teq is the equilibrium temperature. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.
dG = VdP - SdT
(again ignoring X)
For a reaction of melting (like ice water) V is the volume change involved in the reaction (Vwater - Vice) similarly S and G are the entropy and free energy changes dG is then the change in G as T and P are varied
G is (+) for S L at point A (GS < GL) G is (-) for S L at point B (GS > GL) G = 0 for S L at point x (GS = GL)
Pick any two points on the equilibrium curve G = ? at each Therefore dG from point X to point Y = 0 - 0 = 0
dG = 0 = VdP - SdT
dP S = dT V