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Isothermal Expansion of A Perfect Gas

1. An isothermal expansion of a perfect gas at constant temperature results in no change in internal energy but work is done as pressure decreases and volume increases. 2. For a reversible process, the maximum possible work is done and can be calculated using the ideal gas law. For the example given, the reversible work is -4.12 kJ. 3. Statistical thermodynamics defines disorder/entropy as the natural log of the number of possible microscopic arrangements or states that a system can occupy at a given macrostate. Higher disorder or more states corresponds to higher entropy.

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Maria Zvolinskaya
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19 views

Isothermal Expansion of A Perfect Gas

1. An isothermal expansion of a perfect gas at constant temperature results in no change in internal energy but work is done as pressure decreases and volume increases. 2. For a reversible process, the maximum possible work is done and can be calculated using the ideal gas law. For the example given, the reversible work is -4.12 kJ. 3. Statistical thermodynamics defines disorder/entropy as the natural log of the number of possible microscopic arrangements or states that a system can occupy at a given macrostate. Higher disorder or more states corresponds to higher entropy.

Uploaded by

Maria Zvolinskaya
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Isothermal expansion of a perfect gas

n, R, T constant
q
Þ p1V1 = p2V2
(for a perfect gas)

constant temperature (isothermal)


Þ p2 = 1 atm; V2 = 15 L
n = 1 mol; p1 = 15 atm; V1 = 1 L
If the pins are removed what happens?
Note: ∆U = 0 does not mean that
What is the change in internal energy? q or w is 0, only that q = -w;
∆U = U2 - U1 ∝ ∆T Þ ∆U = 0 in fact, w = - p2∆V
e.g., p2 = 1 atm = 101,325 Pa
What is the change in enthalpy?
0 0 w = -101,325 Pa (14 L) (10-3 m3/L)

∆H = H2 - H1 = (U2 + p2V2) - (U1 + p1V1) Þ w = -1.42 kJ q = 1.42 kJ


Þ ∆H = 0
Nils Walter: Chem 260
Work in an isothermal expansion is
p2
pathway dependent
w = - p2 ∆V = -1.42 kJ p1 = 15 atm, V1 = 1 L
p1 = 15 atm p2 = 1 atm w = -1.42 kJ

Pressure
V1 = 1 L V2 = 15 L
T = 298 K T = 298 K w = -4.12 kJ
n = 1 mol n = 1 mol p2 = 1 atm, V2 = 15 L

A truly reversible
process would take an Volume
infinite amount of time
to complete

AAreversible
reversibleprocess
processisisin
inequilibrium
equilibriumat
atall
alltimes
times
V2 perfect gas V2
dV
w = − ò pdV = − nRT ò
V1 V1
V
æ V2 ö AAreversible
w = − nRT lnçç ÷÷ = −4.12 kJ reversibleprocess
processrepresents
represents
the
themaximum possible
ChempV 260work
è V1 ø Nils Walter:
maximum possible pV work
But there’s more: Disorder
-411.15 kJ/mol -240.12 kJ/mol -167.16 kJ/mol
..........
NaCl(s) → Na+(aq) + Cl-(aq)

∅
Hess: ∆rH = å ν∆fH (Prod.) - å ν∆fH (React.)

∅
∆rH = [-167.16 - 240.12 - (-411.15)] kJ/mol = + 3.87 kJ/mol

This is an endothermic reaction - but clearly spontaneous,


as was the endothermic reaction demonstrated in class:

2 NH4SCN(s) + Ba(OH)2• 8H2O(s) → 2NH3 (g) + Ba(SCN)2 (s) + 10 H2O(l)

The reverse reactions are not spontaneous

Qualitatively:
Qualitatively: “Nature
“NaturePrefers
PrefersDisorder”
Disorder”

NaCl(s) “Ordered” → Na+(aq) + Cl-(aq) “Disordered”


Nils Walter: Chem 260
Measuring disorder in thermodynamics:
Statistical thermodynamics
Consider a system with 3 balls --- and 3 bowls:

A possible state of the system is Another possible state is 2 balls in


1 ball in each bowl bowl 1, 1 ball in bowl 2
6 Possibilities 3 Possibilities
#= 3!
#= N! 2! 1! 0!
N1! N2! N3! More
Moreordered
ordered
#= 3! State
State
1! 1! 1!
Or 3 balls in bowl 1 1 Possibility
Disordered
DisorderedState
State #= 3!
3! 0! 0!
Nils Walter: Chem 260 State
Ordered
Ordered State
What the h… does this have to do with a gas?
A B

Gas molecules in two gas bulbs of equal size


Coin Flips
The probability of
1
1
any one molecule being in A is P = 2 ( ) 1
2

2
1 1 1
any two molecules in A is P = • 2 = 4
2 ( ) 1
2
3
1 1 1 1
any three molecules in A is P = • 2 • 2 = 8
2 ( )
1
2

Probability of N molecules in A N consecutive heads


N N
P = ( ) 1
2 ( )
Nils Walter:PChem 1
= 260
2
Measuring disorder in thermodynamics:
Statistical thermodynamics
Consider a system with 3 balls --- and 3 bowls:

A possible state of the system is Another possible state is 2 balls in


1 ball in each bowl bowl 1, 1 ball in bowl 2
6 Possibilities 3 Possibilities

W =3
W =6
3 1
6 1 P= =
P= = 18 6
18 3
Or 3 balls in bowl 1 1 Possibility
W =1
1
=
Nils Walter: ChemP260
18
The statistical definition of disorder =
Boltzmann entropy S
Equation
W = number of microstates or
SS==kkln
lnW
W degeneracy of a macrostate

k = Boltzmann Constant
×10-23 J K-1
1.3805× Þ S has units of J K-1

S accounts for the disorder

W= 5 SS==1.61
1.61kk
W = 10 SS==2.30
2.30kk
S is an extensive function

S is a state function, i.e., the value


of S depends on the state, not on
W = 10 SS==2.30
2.30kk how the state was reached
Nils Walter: Chem 260

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