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We have seen two forms of the first law:

dU =C dT −P dV dU =T dS− P dV

Where C is the heat capacity of the system.

More to come on C later.

So, the internal energy is a function of what two variables?

U = U(T,V)

dU =

∂U ∂T ∂U ∂S

dT −

V

∂U ∂V ∂U ∂V

dV

T

U = U(S,V)

dU =

dS −

V

dV

S

Gay-Lussac Experiment

Upon opening the valve, there is no change in T. What is the significance of this fact? Which form of U do we want?

dU =C V dT − P dV

dU =

∂U ∂T

dT −

V

∂U ∂V

dV

T

Ideal Gas

For an IDEAL GAS:

∂U =0 ∂V T

Which means that for an ideal gas, U(T,V) = U(T). Return to the first homework problem: P A

B V

What is the entropy change during isothermal expansion of an ideal gas piston from A to B?

Ideal Gas

What is the entropy change during adiabatic expansion of an ideal gas piston from A to B?

P

A

B V

Ideal Gas

What is the entropy change during free expansion of an ideal gas from VA to VA+B?

Does no work, transfers no heat, therefore U is constant, which means T is constant. Since the PV state variables are path independent, use the isothermal expansion case to determine the entropy change.

What is entropy?

Why is it useful?

Consider two cubes in a box at different temperatures. A small amount of energy moves from the higher temperature cube to the lower temperature cube.

Thigh

Tlow

S high=−

Q T high

Q S low= T low S total = Q

1 1 − 0 T low T high

What is entropy?

Why is it useful?

Consider two coupled pistons containing an ideal gas at different pressures pushing against each other isothermally.

Phigh

Plow

Q high dS high= T = P high dV T dS total = 1 P − P low dV T high

P low dV dS low=− T

Entropy?

Entropy

Entropy is the opposite of information. The higher the entropy, the less is known about the system.

HW: 2.4, 2.9, 2.10, 2.11, 2.13, 3.6

Mathematical background

∂ ∂z ∂x ∂y

x

∂z = ∂ ∂ y ∂x y

y x

∂z ∂y

x

1 ∂y = ∂z ∂z ∂y x

x

∂y ∂x

z

∂x =−1 ∂z y

Legendre Transformation

x,y ,

Every point on the curve can be described by a unique (x,y) coordinate or a ( , ) coordinate.

y

dy dy = y x − x dx dx

Enthalpy

An example of a Legendre Transformation: How can we write U(S,V) without the V?

U S,

But . . .

∂U ∂V

S

=U S , V −

∂U V ∂V S

From the first law we know that

P=−

∂U ∂V

S

So we call the new function Enthalpy and write

H S , P =U S , V P V

Or simply

H =U P V

**What good is Enthalpy?
**

Adiabatic throttling

Pressure and Volume both change as the system passes the throttle. ∆U = P1 V1 – P2 V2 Since ∆U = U2 – U1, we can rearrange to make U2 + P2 V2 = U1 + P1 V1 H2 = H1

dH

H =U PV dH =dU P dV VdP dH =T dS − P dV P dV VdP dH =T dSVdP

The term V dP can be thought of as non-mechanical work. So the first law still applies:

dH = δQ + V dP

But this time the work term is non-mechanical.

Isobaric Expansion

P A B

V

∆U = ∆Q - ∆W

U2 - U1 = ∆Q - (P2 - P1) V H2 - H1 = ∆Q Where do isobaric processes occur?

Specific Heat

We just determined that under isobaric conditions that H2- H1 = ∆Q We can also calculate the heat change as ∆Q = C∆T Together these imply that

C P=

H 1 ∂H n ∂T T

P

The subscript P indicates constant pressure (isobaric), and the n normalizes the energy per mole. Similarly, under constant volume,

U 1 ∂U CV= n ∂T T

V

**Specific Heat notes
**

CV= Q 1 ∂U = T n ∂T

V

Note that ∆Q is not an exact differential, i.e. the magnitude of ∆Q is path dependent. However the heat capacity is an exact quantity. That is why heat capacities must specify a path, either constant pressure or volume. We had already decided that U was a function of T only (ideal gas). So we can assume:

CV=

1 ∂U n ∂T

Q T

V

dU =n C V dT

Also, don't confuse calculations for entropy and heat capacity.

CV=

V

Q S= T

**∆H during isothermal expansion
**

What is the enthalpy change during adiabatic expansion of an ideal gas piston from A to B?

P

A

B V

H =U PV H =U T n R T

Isothermal implies no change

Gas Constant: R

Lets assume a small temperature change, such that CV and CP can be considered constant.

dU =n C V dT

From the first law we have:

and

dH =n C P dT

Q=dU P dV

Equate Qs, substitute dU and dH . . .

Q=dH −V dP

n C P dT −V dP=n C V dT P dV n C P −C V dT =P dV V dP

C P−C V = n

1 d PV dT

=R

Another constant which occurs frequently is .

CP = CV

You open a valve to fill an evacuated tank with air. The tank is insulated, the air is an ideal gas. What is the temperature of the gas in the tank after it is filled? UF - U0 = -∆W = P0 V0 T0, P0, V0 UF = U0 + P0 V0 = H0 CVTF = CPT0

Homework 2.5, 3.8

p2 T = p1 T 1

2 −1

TF = T0

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