Professional Documents
Culture Documents
Thermodynamics
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 1 / 20
Two questions
dV
Evaluate dP s ?
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 2 / 20
(dV/dP)s = ???
Compressibility of a particular
substance?
Half a Maxwell relation?
Adiabatic change in volume as
pressure increases?
Something to do with Power and
Voltage?
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 3 / 20
Dependent and Independent Variables
In thermodynamic derivations, it is
not obvious what to choose as the
dependent variable.
This is the physics of the question.
The rest is just maths.
Ewe chews
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 4 / 20
Example: The difference in heat capacities, CP − CV
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 5 / 20
Identify terms which are materials properties
∂S ∂S ∂V
CP = T +T
∂T V ∂V T ∂T P
Introducing heat capacity
∂S
CV = T
∂T V
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 6 / 20
Eliminate the unmeasurable
∂S
CP − CV = TV β
∂V T
Recall S is not readily measurable, so use Maxwell to eliminate S.
∂S ∂P ∂P ∂V
= =−
∂V T ∂T V ∂V T ∂T P
and introduce the isothermal bulk modulus and thermal expansivity (again)
∂P 1 ∂V 1
= −V = KV β = K β
∂V T V ∂T P V
∂P
and β = V1 ∂V
K = −V ∂V T ∂T P
CP − CV = TV β 2 K = TV β 2 /κ
CP − CV ∝ V =⇒ extensive quantity.
K is positive for all known substances.
β 2 is positive.
CP > CV , even for negative thermal
expansion.
CV = CP at the density maximum in water.
β is small except for gases. CP ≈ CV : for
solids and liquids often lazily just give
“heat capacity”
Difference is NOT due to work done
expanding the material.
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 8 / 20
Variations in CV and CP
∂CV
What is ∂V ?
T
∂CV ∂ ∂S ∂ ∂S
= T =T
∂V T ∂V ∂T V T ∂T ∂V T V
∂2P
∂ ∂P
= T =T
∂T ∂T V V ∂T 2 V
We can calculate
these directly from equation of state.
∂CP
e.g. ∂P is Zero for Ideal Gas V=RT/P.
T
formally, infinite for a phase transition (volume changes at constant T,P.).
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 9 / 20
Aside: Latent heats and the Lambda Function
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 11 / 20
Increasing energy under pressure
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 12 / 20
The ratio of heat capacities CP /CV
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 13 / 20
The entropy of an ideal gas, again
s = cv ln T + R ln v + s0
Similarly s = cP ln T − R ln P + s0 .
Again, we relate changes in entropy to measurable quantities via the
equation of state.
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 14 / 20
Availability
1904 Prince Piero Ginori Conti. generating electric energy from geothermal steam
∆S + ∆Ssurr ≥ 0
Q
∆S − ≥ 0
T0
Q is heat transferred from the reservoir into the system.
First law for system gives Q = ∆U + P0 ∆V :
∆U + P0 ∆V − T0 ∆S ≤ 0
A = U − T0 S + P0 V
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 16 / 20
Availability A = U − T0 S + P0 V
dA = dU − T0 dS + P0 dV = 0
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 17 / 20
Availability incorporates all potentials
At equilibrium (T = T0 , P = P0 ), dA = 0
If T = T0 & P = P0 A = U − TS + PV ∴ G is minimum
If T = T0 & V = const A = U − TS + const ∴ F is minimum
If S is const. & V = const A = U + const ∴ U is minimum
If S is const. & P = P0 A = U − const + PV ∴ H is minimum
If U is const. & V = const A = const − T0 S ∴ S is maximum
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 18 / 20
Useful Work
We assumed the only work done by the system was in expanding against
the environment P0 ∆V , but heat transfer could produce other useful work.
In that case the First Law becomes
∆U = Q − W = Q − W useful − P0 ∆V (1)
∆U + P0 ∆V − T0 ∆S + W useful = W useful − ∆A ≤ 0
Maximum useful work is Wmax = −∆A. (iff all changes are reversible).
This is also clearly seen if we look at a small differential change of A:
Graeme Ackland Lecture 10: Relationships between properties October 19, 2017 19 / 20
Available for work