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Chapter 4 of Atkins: The Second Law: The Concepts Changes in molecular order occur when a substance freezes or boils.

Consider the phase transitions of water, at transition temperatures Ttrs . For ice water, T trs =

273 K, ice in equilibrium with liquid water at 1 atm; and for boiling water, T trs = 373 K, liquid

Section 4.3 water in equilibrium with vapor at 1 atm

Entropy of Phase Transition water, and in order to match attractive forces between

ice molecules, energy must come from kinetic energy

at the Transition Temperature of the water molecules or the surroundings

Expansion of the Perfect Gas surroundings is reversible since the two phases in the

system are in equilibrium (the forces pushing the ice

towards melting are equal to those pushing the water

Variation of Entropy with Temperature towards freezing) - so phase transition is reversible

It does not matter how the ice melts (what path it takes) since entropy is a

Measurement of Entropy state function. What does matter for this particular expression is that the

system be isothermal . If it was not isothermal, one would have a problem

examining the process in steps – as we shall see…

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 1 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 2

At constant pressure, q = ∆trsH, and ∆ trsH Trouton’s Rule: This empirical observation (see Table 4.2) states that most liquids

the change in molar entropy is ∆ trsS = have approximately the same standard entropy of vaporization,

T ∆vapSo = 85 J K-1 mol-1: so, ∆vapHO = Tb x 85 J K-1 mol-1

For exothermic and endothermic phase transitions: Some Standard Entropies of Vaporization

∆vapHO (kJ mol-1) θboil (oC) ∆vapSO (kJ mol-1)

freezing, condensing Benzene +30.8 80.1 +87.2

CCl4 +30.0 76.7 +85.8

∆ trsH > 0 Exothermic ∆ trsH < 0 Cyclohexane +30.1 80.7 +85.1

∆ trsS > 0 phase transition ∆ trsS < 0 H2S +18.7 -60.4 +87.9

Methane +8.18 -161.5 +73.2

disordered Endothermic ordered Water +40.7 100.0 +109.1

melting, boiling Exceptions:

9 In water, molecules are more organized in the liquid phase (due to hydrogen

Consistent with decreasing disorder: gases > liquids > solids bonding), so a greater change of disorder occurs upon vaporization

9 In methane, the entropy of the gas is slightly low (186 J K-1mol-1 at 298 K) and

in light molecules very few rotational states are accessible at room temperature -

Example (but BE CAREFUL): when compact condensed phase vaporizes associated disorder is low

into a widely dispersed gas, one can expect an increase in the disorder of

the molecules

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 3 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 4

1

Expansion of a Perfect Gas Variation of Entropy with Temperature

The ∆S for an isothermally expanding perfect gas can be written as The entropy of a system at temperature Tf can be calculated from

knowledge of S at initial temperature and heat supplied to make ∆T:

⎛V ⎞

∆S = nR ln⎜ f ⎟ (see lecture 10 notes) ∆S = ∫

f dqrev

⎝ Vi ⎠ i T

(equation applies for reversible or irreversible change, since S is a state When the system is subjected to constant pressure (i.e., the atmosphere)

function - but remember that the value of ∆S must be computed with the during heating, from the definition of constant pressure heat capacity, if

integral of reversible heat divided by T ) the system is not doing expansion work (w =0),then

dqrev = C p dT

Reversible change: ∆Stot=0

The surroundings are in thermal and mechanical equilibrium with system, Then, at constant pressure (or constant volume, replace with CV):

so Cp

S(Tf )= S (Ti ) + ∫

Tf

∆Ssur = -∆S =-nR ln (Vf/Vi) dT

Ti T

Free irreversible expansion (into vacuum): w=0 If Cp is invariant to temperature change

If isothermal, q=0 in this case, and ∆Ssur=0 ⎛T ⎞

with ∆Stot=nR ln (Vf/Vi) S(Tf )= S (Ti ) + C p ln⎜ f ⎟

⎝ Ti ⎠

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 5 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 6

Calculate ∆S when argon at 25oC and 1.00 atm in a container of volume Consider the entropy changes for putting an ice cube in a glass of warm water and

500 cm3 expands to 1000 cm3 and is simultaneously heated to 100oC letting it melt (assume an adiabatic container)

q1 q2 q3

Methodology: Since S is a state function, we can choose a convenient

path from initial to final state: (1) isothermal expansion to final volume,

followed by (2) reversible heating at constant volume to final temperature

Tinitial Tfus Tfus Tfinal

Amount of Ar present is n =pV/RT = 0.0204 mol

Start at Ti

Cp,m (Ar) = 20.786 J K-1 mol-1 (1) Calculate ∆S to cool the water to 0oC by reversibly removing heat, q1, from the

system

(1) Expansion from 500 cm3 to 1000 cm3 at constant T: (2) At Tfus, calculate the amount of heat, q2, to be added to the system to melt the

∆S=nR ln 2.00 =+0.118 J K-1 ice cube

(3) Calculate the difference between the two amounts of heat and add back

remaining heat so that the total heat lost or gained is zero (adiabatic system)-

(2) Reversible heating from 25oC to 100oC at constant V: determine the entropy change in this process

∆S=(0.0204 mol) x (12.48 J K-1) x ln (373 K /298 K)

=+0.057 J K-1 At each step, the infinitesimal entropy change for the system, dS, is just dq divided

by the T. For the cooling and heating of water, integrate over the temperature

range, since the temperature is not constant.

Overall entropy change: ∆S =+0.118 J K-1+0.057 J K-1=+0.175 J K-1

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 7 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 8

2

Entropy Change of Melting Ice, 2 Entropy Change of Melting Ice, 3

Step 1: Entropy decrease for the system as the water is cooled How do we know Tf ? System is adiabatic so the total heat must be zero, or q3 =

-(q1+q2), giving Tf=Tfus+q3/Cp

⎛T ⎞

∫ ∫

T fus dqrev T fus dT

∆S1 = = Cp = C p ln⎜ fus ⎟

Ti T Ti T ⎝ Ti ⎠ Is the process spontaneous? (We know intuitively that it is - sticking an ice cube

into warm water melts the ice cube!!) How do we prove this?

Step 2: Melt the ice at the temperature of Tfus= 0oC (qfus = q2) Show that the total entropy change (the system plus the surroundings) is positive.

The entropy change of the system we know is:

q ∆ H ∆S1+ ∆S2+ ∆S3

∆S2 = fus = fus

T T Lecture Problem:

Try the above steps for 5.0 g of ice at 60.oC in 110. mL of water

Step 3: Balance the heat by (in this example) adding an amount of heat With Cp,m of water of 75.6 J K-1 mol-1 and ∆fusH = 6.01 kJ mol-1.

-(q1+q2) back into the glass (ice cube melted completely), remove more Calculate ∆S1 , ∆S2 , ∆S3, ∆S, Tf

heat to cool the glass to 0oC than you would have to add in order to melt

the ice -- increase in entropy: Note that since the system is adiabatic, ∆Ssur=0 (the water is part of the system).

⎛T ⎞ Change in

∆S3 = C p ln⎜⎜ f ⎟⎟ Extra Credit Lecture Problem: Use the same conditions as above, except try the

notes calculation for an isothermal system

⎝ Tfus ⎠

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 9 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 10

Some changes in state and associated entropy changes for the system, Entropy of a system at temperature T can be related to entropy at T = 0

for an infinitessimal change in entropy, dS =dqrev/T: by measuring heat capacities at different temperatures, and evaluating

Cp

S(Tf )= S (Ti ) + ∫

Tf

Vary the temperature at constant volume (CV independent of T): dT

Ti T

⎛T ⎞

∆S = ∫ = ∫

T f dq T f C dT

v

= Cv ln⎜ f ⎟ The entropy of transition, ∆trsS = ∆trsH/Ttrs, is added for each phase

Ti T Ti T ⎝ Ti ⎠ transition between T = 0 and T (temperature of interest)

Vary the temperature at constant pressure (Cp independent of T):

For example, if substance melts at Tf and boils at Tb, entropy above Tb is

T f C p dT ⎛T ⎞

∆S = ∫ = ∫

T f dq

= C p ln⎜ f ⎟ C p (s) ∆ H

S(T ) = S (0) + ∫

Tf

Ti T Ti T ⎝ Ti ⎠ dT + fus

0 T Tf

For isothermal expansion of a perfect gas

⎛V ⎞ ⎛p ⎞ C p (l) ∆ H C p (g)

+∫ ∫

Tb T

∆S = nRln⎜ f ⎟ = nRln⎜⎜ i ⎟⎟ dT + vap + dT

Tf T Tb Tb T

⎝ Vi ⎠ ⎝ pf ⎠

What if both T and P or T and V change? Simple, use two steps! First All of the quantities can be determined from calorimetry excepting S(0),

change the T holding either V or P constant, then change V or P at and integrals can be evaluated analytically (see next)

constant T (depending on what you are given).

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 11 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 12

3

Measurement of Entropy, 2 Example: Calculating Entropy

Plot (a) shows the variation of Cp/T with sample Consider standard molar enthalpy of N2(g) at 25 o C, calculated from the

temperature. The area under the curve of Cp/T as following data:

a function of T is required. However, since dT/T =

d ln T, can also evaluate area under Cp vs. ln T. S mo (J K -1 mol -1 )

Debye exptrapolation 1.92

Integration from 10 - 35.61 K 25.25

Plot (b) shows the entropy of the system varying Phase transition at 35.61 K 6. 43

with temperature, which is equal to the area under Integration from 35.61 - 63.14 K 23.38

the curve up to the corresponding temperature, Fusion at 63.14 K 11.42

plus entropy of each phase transition passed. Integration from 63.14 - 77.32 K 25.25

Vapourization at 77.32 K 72.13

Integration from 77.32 - 298.15 K 39.20

One problem with measuring ∆S is measuring Cp Correction for Gas Imperfection* 0.92

at low T nearT = 0: Debye extrapolation: It has

been shown that at temperatures near T = 0, the Total 192.06

heat capacity is approximately proportional toT3 S mo (298.15 K) = S mo (0) + 192.1 J K -1 mol -1

(Cp = aT3 as T → 0)

*See section 20.5 of book - failure of hard sphere approximation

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 13 Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 14

is 0.52 J K-1mol-1. What is the molar entropy at that temperature?

Because temperature is low, we can assume that heat capacity varies with

temperature as aT3:

aT 3

S (T ) = S (0) + ∫ dT = S (0) + ∫

Tf Tf

T 2 dT

T 0 0

1 1

3 3

It turns out that the final result can be expressed in terms of a heat

capacity at constant pressure…

1

Sm (12K ) = Sm (0) + C p (12K ) note small change

3

= Sm (0) + (0.52 J K -1 mol-1 )= Sm (0) + 0.17 J K -1 mol-1

1

3

Prof. Mueller Chemistry 451 - Fall 2003 Lecture 11 - 15

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