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Chemical Engineering Thermodynamics-I

Engr. Prof. Dr. Mahmood Saleem

Institute of Chemical Engineering & Technology University of the Punjab, Lahore

4th Semester 2011

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.




Course Outline Fundamental Concepts
Basic Definitions in thermodynamics Laws of thermodynamics Volumetric properties- Equations of state Property relations for pure substances

Thermodynamics applied to practical situations:

Concepts of equilibrium
Phase Equilibrium Reaction Equilibrium

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

Submit an assignment within next 2 weeks (hand written) 7<pages>10

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

m, V, U, E

T, P, , u, e

State, Equilibrium, Processes

State or Condition of a System Equilibrium - System in balance, NO Changes
thermal/temperature balance - no HEAT transfer/adiabatic mechanical/pressure balance - no WORK transfer phase - no change of phases chemical - no change of spices

Pressure Scales
Gauge pressure Local atm. pressure Standard atm. pressure Vacuum pressure

101.325 kPa(abs) 14.696 psi(a) 760 mmHg(a) 29.92 inHg(a)

Local atm. 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 is not the equivalent of the system energy Historical background

Temperature Measurement Devices

thermocouples, resistive temperature devices (RTDs and thermistors), infrared radiators, bimetallic devices, liquid expansion devices, and change-of-state devices.

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).

Fixed (reference) points Interpolation between the fixed points

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

2nd Law of thermodynamics

Definition Mathematical formulation Applications

3rd Law of thermodynamics

Concepts of Equilibrium
Equilibrium Mathematical formulation Applications
Phase equilibrium Reaction equilibrium


a system: The surroundings:

Some portion of the universe that you wish to study The adjacent part of the universe outside the system

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.

Gibbs Free Energy

Gibbs free energy is a measure of chemical energy All chemical systems tend naturally toward states of minimum Gibbs free energy G = H - TS
G = Gibbs Free Energy H = Enthalpy (heat content) T = Temperature in Kelvins S = Entropy (can think of as randomness)

a Phase: a mechanically separable portion of a

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

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

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

In our calorimeter we can then determine H for the reaction:

Si (metal) + O2 (gas) = SiO2

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)

Then we can use G = H - TS to determine G of quartz = -856,288 J/mol

For other temperatures and pressures we can use the equation:

dG = VdP SdT

(ignoring X for now)

where V = volume and S = entropy (both molar)

We can use this equation to calculate G for any phase at any T and P by integrating




1 P1

P2 P1


T2 T1


If V and S are constants, our equation reduces to:

GT2 P2 - GT1 P1 = V(P2 - P1) - S (T2 - T1)

which arnt bad!

In Worked Example 1 we used

GT2 P2 - GT1 P1 = V(P2 - P1) - S (T2 - T1)

and G298, 0.1 = -856,288 J/mol to calculate G for quartz at several temperatures and pressures
Low quartz P (MPa) 0.1 500 0.1 500 T (C) 25 25 500 500 Eq. 1 G (J) eq. 1 -856,288 -844,946 -875,982 -864,640 G(J) -856,648 -845,362 -890,601 -879,014 SUPCRT V (cm3) 22.69 22.44 23.26 23.07 S (J/K) 41.36 40.73 96.99 96.36

Agreement is quite good (< 2% for change of 500o and 500 MPa or 17 km)

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.

Does the liquid or solid have the lowest G at point A?

What about at point B?

Figure 1-2. Schematic P-T phase diagram of a melting reaction. Winter (2001) An Introduction to Igneous and Metamorphic Petrology. Prentice Hall.

The phase assemblage with the lowest G under a specific set of conditions is the most stable

Free Energy vs. Temperature

dG = VdP - SdT at constant pressure: dG/dT = -S Figure 5.3. and Because S must be (+) G forRelationshipatbetween Gibbs free energythe a solid constant temperature for aphase pressure. T is equilibrium temperature. Winter (2001) An Introduction to Igneous and decreases as T increases Metamorphic Petrology. Prentice Hall.

Would the slope for the liquid be steeper or shallower than that for the solid?

Free Energy vs. Temperature

Slope of GLiq > Gsol since

Ssolid < Sliquid

A: Solid more stable than liquid (low T) B: Liquid more stable than solid (high T) Slope P/T = -S Slope S < Slope L Equilibrium at Teq GLiq = GSol

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.

Now consider a reaction, we can then use the equation:

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)

G for any reaction = 0 at equilibrium

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