10/28/2016

The Second Law The Second Law

• The entropy change for a system is the change in • Alternative statements:
heat absorbed during a reversible process divided
by the temperature of that change. dq irrev
dq rev ΔSsys ≥ “Heat cannot be
T
T spontaneously transferred
from a cold object to a hot
object.”
• Formally, the second law of thermodynamics
states that for any change the total entropy “Entropy must increase or
remain constant in an isolated
change is greater than or equal to zero: system.”
dq “You can’t create a perpetual
tot sys surr , or tot motion machine.”
T

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Standard State Entropies Summary: Entropy Changes

• Same idea as enthalpies: define a standard state • Temperature (also true for CV at const. V)
and operate relative to that T2
0 S T2 —S T1 = CP ln
obs ref T1

• Any property of is a property of 0 (or 0 ): • Phase Change

∆Ht r Tt r
0 0 2 ∆St r Tt r =
2 1 P
Tt r
1
• Pressure Change
– Approximately zero for solids, liquids
• Reference state for entropy is at 0 K (more on P2 V2
that later) – Ideal gasses at constant T: ∆S = —nRln P1
= nR ln V1

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Molecular Interpretation of Entropy Predicting Entropic Changes

• Using concept of disorder, we can often predict
sign of entropy
2H2O(g)  2H2(g) + O2(g)
0 = –1 –1

Many configurations for gas molecules Fewer configurations for gas molecules
• Hard to predict total changes in aqueous solution
• Entropy is a measure of the number of (system + surroundings) because water can
microscopic configurations a system can have become ordered or disordered
while maintaining the same macroscopic NH4+(aq)  H+(aq) + NH3(aq)
0 –1
properties (volume, temp., density, etc.) = -1

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Is the Second Law Always True? Introduction: Gibbs Energy

• Consider a microscopic fluctuation, caused by • Recall: Any combination of state variables is also
a state variable
random (Brownian) motion:

• Any change in G can be represented as before:

• Additionally, let’s no longer assume only P, V

• The red molecules are no longer evenly work:
∗
distributed ex rev

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Implications: ΔG at const. T, P Implications: ΔG at const. T, P

• In a chemical reaction, some work is required • If ΔG = 0 for a process:
to change volume a small amount – System can do no (non‐PV) work on surroundings
– Equilibrium state
– This is not useful work to a chemist
• If ΔG > 0 for a process:
– Work done by surroundings is negative; work is
• ΔG is the (useful) work done by the system for required to complete process
a given process – Process it not spontaneous (it needs work)
– The inverse, ‐ΔG is the maximum amount of useful • If ΔG < 0 for a process:
work the system can do on the surroundings – Work done on surroundings is positive
( ∗ )
rev
– Irreversible work is not as efficient – Process occurs spontaneously (no work needed)

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Implications: ΔG at const. T, P Multidimensional Functions

• If we know and for any process at • Simple “3D” Function:
0 0) 2 2
constant T, P (or and

• What’s “the
and derivative?”
0 0 0

• Does our 2D definition

• Follows directly from the definition of G even make sense?
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Partial Derivative Example #1 Partial Derivative Example #2

2 2, 6ƒ 2 2
6s y

y = ‐1.05 to ‐0.95 y = ‐0.8 to ‐0.7 y = ‐0.55 to ‐0.45 y = ‐0.05 to 0.05

x = ‐1 to 1 x = ‐1 to 1 x = ‐1 to 1 x = ‐1 to 1

• Looking at small slices along y, the slope in the x‐z plane is

the same
• Key result: Partial derivatives tell us the slope in a specified
plane!
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Partial Derivative Example #2 Partial Derivative Example #2

2 2, 6ƒ 2
• First partial derivative • First partial derivative
6s y with respect to x (y with respect to y (x
constant): constant):
∂ƒ ∂ƒ
= 2xy + y 2 = x 2 + 2xy
∂x y ∂y x

• Second partial derivative • Second partial derivative

y = ‐1.05 to ‐0.95
x = ‐1 to 1
y = ‐0.55 to ‐0.45
x = ‐1 to 1
y = ‐0.05 to 0.05
x = ‐1 to 1
y = 0.95 to 1.05
x = ‐1 to 1
with respect to y (x constant): with respect to x (y
constant):
• Partial derivative depends on y, so slope in x‐z plane will ∂ ∂ƒ ∂ ∂ƒ
depend on which x‐z plane = 2x + 2y = 2x + 2y
∂y ∂x ∂x ∂y x
• Just because y was constant while taking the derivative, y s y
doesn’t mean it has to be constant afterward!
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Partial Derivative Example #2 Self Test: Ideal Gas Law

• Consider the ideal gas law:
–1
It’s true in general that:

• Calculate the following:

y x x
y
∂V ∂V
and
∂ P T,n ∂ T P,n

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Differentials Differentials Example

• If we know y0 = f(x0) what’s the change in y0 if x0 is • If h(x) = f(x)g(x), can we find dh?
changed a little (dx)? dh d
= ƒ x g x
dx dx
0 0 0 dƒ dg
dh = dx g x + ƒ x dx
dx dx
Differentials relate a small
• Therefore: change in one variable (dy) • Thus, it’s true that:
to a small change in other
variable(s) (dx)
dh = dƒ · g x + ƒ x · dg = ƒ x dg + g x dƒ

• And:
d PV = PdV + VdP
• What’s the corresponding result for N‐dimensions?

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Multidimensional Differentials But I Don’t Like Calculus…

• If f = f(x, y, z), we can write the exact differential • Last class, we determined that (for reversible
of f as: processes, only PV work):

In other words, E is
a “natural function”
• For smaller changes: of S and V.
y,z x ,z x ,y

• This is a mathematical fact, not a thermodynamic • Combine the math with the science:
one (shown without proof), but it must apply to ∂E and ∂E
all functions in thermodynamics ∂S V ∂V S

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Summary: Gibbs Energy Changes Summary: Gibbs Energy Changes

• To calculate changes in Gibbs energy at • If ΔS, ΔH constant vs. T:
constant P use: 2 1 2 1
∆G T2 ∆G T1 1 1
– All our tricks for entropy, enthalpy apply T2 T1 T2 T1
– Useful for calculating standard state reactions
• Phase transitions: t r
• As a last resort use • Chemical reactions behave like enthalpy, entropy
(why?)
P2 T2
• Pressure changes
P1 T1 – Solids, liquids: ∆G P2 —∆G P1 = ∆V(P2 —P1)
– Where ΔX = Xproducts ‐ Xreactants – Ideal gasses: ∆G P2 —∆G P1 = ∆nRT ln
P2
P1

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