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Thermodynamics

Thermodynamics is the scientific study of the interconversion of heat and other kinds of energy.
State functions are properties that are determined by the state of the system, regardless of how that condition was achieved.

energy , pressure, volume, temperature

DE = Efinal - Einitial DP = Pfinal - Pinitial DV = Vfinal - Vinitial DT = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2 is the same even though they took different paths.
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First law of thermodynamics energy can be converted from one form to another, but cannot be created or destroyed -also known as Law of Conservation of Energy

Another form of the first law for DEsystem

DE = q + w
DE is the change in internal energy of a system q is the heat exchange between the system and the surroundings w is the work done on (or by) the system

DEsystem + DEsurroundings = 0
or

when a gas expands against a constant external pressure

DEsystem = -DEsurroundings

w = -PDV

C3H8 + 5O2

3CO2 + 4H2O

Chemical energy lost by combustion = Energy gained by the surroundings 3 system surroundings

A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L at constant temperature. What is the work done in joules if the gas expands (a) against a vacuum and (b) against a constant pressure of 3.7 atm? w = -P DV (a)

Enthalpy and the First Law of Thermodynamics

DE = q + w

At constant pressure (Cp):

Therefore

q = DH and w = -PDV

DE = DH PDV, or

DV = 5.4 L 1.6 L = 3.8 L

P = 0 atm

DH = DE + PDV

W = -0 atm x 3.8 L = 0 Latm = 0 joules (b)

DV = 5.4 L 1.6 L = 3.8 L

P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 Latm w = -14.1 Latm x 101.3 J = -1430 J 1Latm

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At constant volume (Cv): No expansion No v w = -PDV, w=0

Reversible and iireversible

DE = q + w, therefore DE = q

Reversible - system and surroundings cannot return to their original conditions when the process is done - System is not in equilibrium

Irreversible The forward and backward reaction still occur at constant rate System in equlibrium

Isothermal & Adiabatic

Isothermal Process conducted at constant temperature Lead to an Increasing in volume

Adiabatic No heat enters or leave the system, q=0 Lead to an Increasing in volume

Second Law of Thermodynamics

Entropy, spontaneity, Gibbs Free Energy

W= nRT ln (V1/V2) E=0, W=q H=0

w = -PDV E = -PDV= nCV T

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Spontaneous Physical and Chemical Processes

A waterfall runs downhill A lump of sugar dissolves in a cup of coffee At 1 atm, water freezes below 0 oC and ice melts above 0 oC Heat flows from a hotter object to a colder object A gas expands in an evacuated bulb Iron exposed to oxygen and water forms rust spontaneous nonspontaneous nonspontaneous spontaneous

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Does a decrease in enthalpy mean a reaction proceeds spontaneously? Spontaneous reactions CH4 (g) + 2O2 (g) H+ (aq) + OH- (aq) H2O (s) NH4NO3 (s) CO2 (g) + 2H2O (l) DH0 = -890.4 kJ/mol H2O (l) DH0 = -56.2 kJ/mol

Entropy (S) is a measure of the randomness or disorder of a system. order S DS = Sf - Si

If the change from initial to final results in an increase in randomness

disorder

Sf > Si

DS > 0

H2O (l) DH0 = 6.01 kJ/mol

H2O

For any substance, the solid state is more ordered than the liquid state and the liquid state is more ordered than gas state Ssolid < Sliquid << Sgas
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NH4+(aq) + NO3- (aq) DH0 = 25 kJ/mol H2O (s)

H2O (l)

DS > 0

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Entropy

Processes that lead to an increase in entropy ( DS > 0)

W = number of microstates S = k ln W DS = Sf - Si DS = k ln Wf Wi

Wf > Wi then DS > 0 Wf < Wi then DS < 0

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Example: Br2(l)

Br2(g)

Example: I2(s)

I2(g)

How does the entropy of a system change for each of the following processes? (a) Condensing water vapor Randomness decreases Entropy decreases (DS < 0)

(b) Forming sucrose crystals from a supersaturated solution Randomness decreases Entropy decreases (DS < 0) (c) Heating hydrogen gas from 60 0C to 800C Randomness increases (d) Subliming dry ice DS > 0 DS > 0
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Entropy increases (DS > 0) Entropy increases (DS > 0)

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Randomness increases

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Entropy State functions are properties that are determined by the state of the system, regardless of how that condition was achieved. Examples: energy, enthalpy, pressure, volume, temperature, entropy Review

Potential energy of hiker 1 and hiker 2 is the same even though they took different paths.

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First Law of Thermodynamics

Factors that Increase the entropy value:

Changes in state:
solid liquid Liquid gas solid gas solid or liquid aqueous state (the dissolving process )

Energy can be converted from one form to another but energy cannot be created or destroyed.

Second Law of Thermodynamics The entropy of the universe increases in a spontaneous process and remains unchanged in an equilibrium process. Spontaneous process: DSuniv = DSsys + DSsurr > 0

An increase in the number of moles.

If the product side of the equation has more moles than the reactant side, the system has become more random; more particles moving about is a more random state than fewer particles moving about.

NonSpontaneous process: DSuniv = DSsys + DSsurr < 0 Equilibrium process: DSuniv = DSsys + DSsurr = 0

Increasing the temperature.

An increase in temperature, caused by an increase in heat energy, increases molecular motion which in turn increases the degree of randomness

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Entropy Changes in the System (DSsys)

The standard entropy of reaction (DS0 rxn ) is the entropy change for a reaction carried out at 1 atm and 250C.
aA + bB DS0 rxn = [ cS0(C) + cC + dD dS0(D) ] - [ aS0(A) + bS0(B) ]

Entropy Changes in the System (DSsys)

When gases are produced (or consumed) If a reaction produces more gas molecules than it consumes, DS0 > 0. If the total number of gas molecules diminishes, DS0 < 0. If there is no net change in the total number of gas molecules, then DS0 may be positive or negative BUT DS0 will be a small number.

DS0 = S nS0(products)- S mS0(reactants) rxn

Example:

What is the standard entropy change for the following reaction at 25 0C? 2CO (g) + O2 (g) 2CO2 (g) S0(CO) = 197.9 J/Kmol S0(O2) = 205.0 J/Kmol DS0 DS0 rxn rxn = 2 x S0(CO2) [2 x S0(CO) + S0 (O2)] = 427.2 [395.8 + 205.0] = -173.6 J/Kmol 23 S0(CO2) = 213.6 J/Kmol

What is the sign of the entropy change for the following reaction? 2Zn (s) + O2 (g) 2ZnO (s) The total number of gas molecules goes down, DS is negative.
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Entropy Changes in the Surroundings (DSsurr)

Third Law of Thermodynamics The entropy of a perfect crystalline substance is zero at the absolute zero of temperature.

S = k ln W W=1 S=0 Exothermic Process DSsurr > 0 Endothermic Process DSsurr < 0
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Gibbs Free Energy

Spontaneous process: Equilibrium process: DSuniv = DSsys + DSsurr > 0 DSuniv = DSsys + DSsurr = 0

The standard free-energy of reaction (DG0 rxn) is the freeenergy change for a reaction when it occurs under standardstate conditions.
aA + bB DG0 rxn = [ cDG0 f (C) + dDG0 f cC + dD bDG0 (B) ] f

Gibbs free energy (G) DG < 0 DG > 0 DG = 0

For a constant temperature and constant pressure process: DG = DHsys -TDSsys

(D) ] - [ aDG0 (A) + f

- S mDG0 (reactants) DG0 = S nDG0 (products) rxn f f Standard free energy of formation (DG0 ) is the free-energy f change that occurs when 1 mole of the compound is formed from its elements in their standard states. DG0 of any element in its stable form is zero. f
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The reaction is spontaneous in the forward direction. The reaction is nonspontaneous as written. The reaction is spontaneous in the reverse direction. The reaction is at equilibrium.

What is the standard free-energy change for the following reaction at 25 0C? 2C6H6 (l) + 15O2 (g) DG0
rxn =

12CO2 (g) + 6H2O (l)

nDG0
f

(products) - S mDG0 f (reactants)

0 0 0 DGrxn = [12DG0 f (CO2) + 6DG f (H2O)] - [ 2DG f (C6H6) ] 0 DGrxn = [ 12x394.4 + 6x237.2 ] [ 2x124.5 ] = -6405 kJ/mol

Is the reaction spontaneous at 25 0C? DG0 = -6405 kJ/mol < 0 spontaneous

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Temperature and Spontaneity of Chemical Reactions

D G = D H - TD S

CaCO3 (s)

CaO (s) + CO2 (g) Equilibrium Pressure of CO2

DH0 = 177.8 kJ/mol DS0 = 160.5 J/Kmol DG0 = DH0 TDS0 At 25 oC, DG0 = 130.0 kJ/mol DG0 = 0 at 835 oC

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Gibbs Free Energy and Phase Transitions

DG0 = 0 = DH0 TDS0

H2O (l) DS =

H2O (g) DH 40.79 kJ/mol = T 373 K = 1.09 x 10-1 kJ/Kmol = 109 J/Kmol
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