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Arvind Agarwal Department of Mechanical and Materials Engineering Florida International University
Universe
System Closed
No matter enter or leaves but energy can go in or out Boundaries may expand/contract due to work done by or on the system
Surroundings Open
Matter is allow to flow in or out
Work (W)
Transform can occur by all others forms of energy (elect, magnetic, mech)
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Convention
When heat goes into the system from surrounding Q > 0 Q Heat (Q) is energy in transit due to temp. difference (T). Q is a flow quantity and not stored by the system. System stores thermal/heat energy and not heat. Heat Energy is referred as Enthalpy (H)
Enthalpy (H)
Heat (Q) is transfer across the boundary of a system due to temperature differential (T) between system and surroundings. Note: System does not contain heat (Q) but Heat Energy (H) . Heat is energy in transit. Heat Energy is also referred as Enthalpy (H)
Internal Energy
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Total Energy can be divided as = Kinetic Energy + Potential Energy + Internal Energy Thus, Total Energy= Internal Energy (U) Internal Energy (U) is due to inherent qualities (motion of atoms and molecules in the matter) as well as environmental variables (temp, pressure, elec. field, mag U= f (material properties, composition, pressure ,temperature)
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State Functions
Thermodynamics properties DO NOT depend on path, but depended on states. S, G, U all are state functions. Work done Internal Energy NOT a state function State function
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Work
In contrast to U, Work is not a state function Work is path dependent (Path function represented by i.e. W) Similarly, Q (heat) is also path dependent and written as Q But loosely speaking we keep on writing Q = dQ and W=dW
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First Law :
To derive practical benefits of this law, we are creating an accounting system needs defining various thermodynamic properties and rules.
Conservation of Energy
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dQ
dW
dQ
dW
dU= dQ dW dW Expansion Work done BY the system = PdV Expansion: dV= V2- V1 V2> V1 dV> 0 PdV> 0 dU= dQ PdV Same
So no difference just follow one??
dU= dQ + dW dW Contraction Work done ON the system = PdV Contraction: dV= V2- V1 V2< V1 dV<0 PdV<0 dU= dQ + (-PdV) dU= dQ PdV
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Enthalpy (H)
Heat (Q) is transfer across the boundary of a system due to temperature differential (T) between system and surroundings. Note: System does not contain heat (Q)but Heat Energy (H) . Heat is energy in transit. Heat Energy is also referred as Enthalpy (H)
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Enthalpy
Q= dU + PdV (from First Law) = d(U+PV) at constant pressure Thus, Q= dH at constant pressure H= U + PV is defined as enthalpy H<0 Exothermic H>0 Endothermic
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Enthalpy
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2.
Extensive properties (mass, volume, internal energy) depend upon sample size. Intensive properties (temperature, pressure, density, specific volume) do not depend upon the sample size.
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Specific Properties
Properties per unit mass (kg or mole) are specific properties. E.g. U, V, G, Cp, Cv Per Mole properties are called Molar properties
Question 1: Are specific properties intensive or extensive? Question 2: what is the specific volume of water? Density = 1g/cc at 298 K Answer: 10 exp 3 m3/kg
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Heat Capacity
Energy regard to increase temperature of a body by 1K. Specific Heat Capacity: Energy to raise the temperature of 1 gm of substance by 1 K. Molar Heat Capacity: Energy to raise the temperature of 1 mol of substance by 1 K.
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Heat Capacity
There are two definitions for vapors and gases: Cp = Specific heat capacity at constant pressure, i.e. Cv = Specific heat capacity at constant volume, i.e.
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Most of the metallurgical procedures are at constant pressure rather than constant volume At constant pressure Q = dH
T2 T2
dH = Cp dT
T1 T1
Kirchoff Eq.
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T2
H2 H1 = Cp dT
T1 T2
H2(T)= H10 + Cp dT
T1
Enthalpy
at absolute zero cant be defined. But we do need a reference point. So, we chose
H10 : Reference State (298 K, 1 atm) occurs when elements exist in equilibrium condition E.g. Diatomic O2, pure Ag, pure Al, pure Cu
H2(T)= H10 +
T1
[Cp
product
+Cp react ] dt
Hesss Law
If a reaction is carried out in a several steps, H of the reaction will be equal to sum of the enthalpy changes for the individual step.
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Latent Heat
Heat needed to change the state of matter S L V Lfusion: quantity of heat energy released when 1 unit weight of a substance solidifies without change the temperature
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First Law dU = dQ + dW dU = dQ PdV dQ dQ = dU + PdV dQ = d(U + PV) If P is constant dQ = dH H= U + PV dW Heat Energy = Enthalpy at constant pressure H< 0 Exothermic (E.g. Thermite reaction) H> 0 Endothermic
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dH = CpdT
T1 T1
Cp = f(t)
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Hesss Law
Hesss Law: If a reaction is carried out in a series of steps, H for the total reaction will be equal to the sum of Hi for each step.
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Heat of Reaction
Heat of reaction: is the heat involved or absorbed when reactants react completely to form products. (Unit: - per mole of any reactant or product) A+B C+D Heat of = Heat product - Heat of reactants reaction
Example 1 CH4 + 2O2 CO2 + 2H2O (g) H0reaction = 2H0H2O + H0CO2 - 2H0O2 - H0CH4 0 H0H2O = -241.8 KJ H0CO2 = -393.5 KJ H0CH4 = -74.8 KJ H0reaction = -802 KJ at 298 K
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Heat of Formation
The heat of formation of a compound (per mole) is the heat evolved or absorbed (i.e. change in enthalpy) when 1 mole of compound forms from its constituents elements or substances e.g. Ni(s) + O2(g) = NiO (s)
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Heat of Formation
Heat of formation = f(temp, pressure, chemical state of reactants and products) Hence, we define heat of formation at standard state I.e. 298 K and 1 Atm. Heat of formation of a compound from its standard state is called Standard Heat of Formation. It is denoted by H0298. i.e. H0298, M for a metal M
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Convention
<M> solid {M} liquid (M) gas Or Ms, ML, MG.
Major Assumption
Enthalpy (H0298 )of O2 at reference state = 0 Enthalpy (H0298 )of pure substances at reference state = 0
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If pure elements/substances are assumed to have zero enthalpy at reference state their compound must have some other values. Example C + O2 CO2 (at 298 K) H react = npproducts nrreaction = Hco2 - Hc - Ho2 0 0 = -393.5 KJ/mol reference state
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Example 3
Page 10, Example 1.C, Dube Upadhyaya Book About <Pb> + (O2) = <PbO>
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Reversible Process
Reversible Process: is that which haven taken place could be reversed and in doing so leaves no change is system or surrounding. (This may
happen if there is no friction, no unrestrained expansion and heat transfer only due to infinitesimal temperature difference)
Irreversible Process
Most of the natural processes are irreversible. For an irreversible (I.e. spontaneous process) S + S >0
system surrounding
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Entropy
State Function (Proof beyond this course) Extensive Property (i.e. depends on mass or # of moles). Units: Cal/deg/mole or Joules/deg/mole
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