Chapter 7: Thermodynamic

Driving Forces
Thermodynamics is Two Laws
and a Little Calculus

I. Definitions
Thermodynamic system - what we study
Open: can exchange U, V, n
Closed: can exchange U, V, but not n
Isolated: cannot exchange U, V, n

Surroundings - everything else

Boundaries
Semipermeable: allows some atoms to pass
Adiabatic: allows no heat to pass

Phase: homogeneous; uniform in p, T, [A]

More Definitions
Property: measurable of a system
Extensive = function of n, N, V
U, S, H, G

Intensive function of n, N
T, P, , [A]

Review
Degree of Observation
Freedom ( max W)

Driving
Force

Ex. 2.2 V
pressure

As V increases,
gas expands.

Ex 2.3 particle
diffusion exch Nj

As {Nj} increases, Chem

potential,
gases mix and
particle distrib j
more uniform

Ex. 3.4

Heat flows until T T

is uniform

II. Fundamental Thermodynamic

Equations: Entropy
S(U, V, N1, N2, )
dS = (S/U)V,NdU + (S/V)U,NdV +
(S/Nj)V,U,Ni dNj
Eqn 7.1
dS = T-1 dU + pT-1 dV - j T-1 dNj Eqn 7.5
Note: dV, dNj, dU are differences in the
degrees of freedom (DegF). p, j, T are
the driving forces. As driving forces (DF)
become more uniform, d(DegF) 0.

Fundamental Thermodynamic
Equations: Energy
U(S, V, N)
dU = (U/S)V,NdS + (U/V)S,NdV +
(U/Nj)V,S,Ni dNj
Eqn 7.2
dU = TdS - pdV + j dNj Eqn 7.4
Note: (U/S)V,N = T means that the
increase in energy per increase in entropy
is positive; as S increases, so does U and
in proportion to T.

III. Equilibrium: dS = 0
Identify system, variables (DegF),
constants
Identify constraints, relationships
Maximize total entropy
Apply constraint
Combine and rearrange to find
requirement for equilibrium

Thermal Equilibrium (Ex. 7.2)

System = isolated = Object A (SA, UA, TA) +
Object B (with similar properties); variables
= UA, UB; constant = V, N ST(U) = SA +
SB = S(UA, UB)
UT = UA + UB = constant constraint dU
= dUA + dUB = 0 or dUA = - dUB
To maximize entropy: dST= 0 =
(SA/UA)V,NdUA + (SB/UB)V,NdUB
(SA/UA)V,N = (SB/UB)V,N 1/TA = 1/TB

Thermal Equilibrium (2)

What does this mean? 1/TA = 1/TB
TA = TB
In order to maximize entropy, energy or
heat will transfer until the temperatures
are equal.
Will heat flow from hot to cold or vice
versa? Check dST = (1/TA - 1/TB)dUA

Mechanical Equilibrium (Ex. 7.3)

Complete

Chemical Equilibrium (Ex. 7.5)

Complete

Two Laws of Thermodynamics

First Law
dU = q + w
dU = T dS p dV (for closed system)
Second Law
dS = q/T

More Definitions
State variables (state functions)
Process variables(path functions)
Quasi-static process: such that properties
f(time, process speed)
Reversible process: special case of quasistatic such that can be reversed with no
entropy change (ideal case)
Thermodynamic cycle: initial = final state

IV. Applications of Fundamental

Thermodynamic Equations
Reversible and Irreversible
Work w = -pext dV (quasi-static process)
V = 0
p = 0
T = 0
q=0

Entropy
Cycles

isobaric
isothermal
adiabatic