School of Physics and Astronomy Junior Honours Thermodynamics

Lecture TOPIC 4
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GJA 2013-2014

(Finn: 3.1, 3.2, 3.3, 3.4, 3.6)

Synopsis: Internal energy: heat capacities and the First Law of Thermodynamics. FIRST LAW OF THERMODYNAMICS: Conservation of Energy Clausius: In all cases in which work is produced by the agency of heat, a quantity of heat is consumed which is proportional to the work done; and conversely, by the expenditure of an equal quantity of work an equal quantity of heat is produced.

INTERNAL ENERGY Joules experiments (1840-1849) conrmed the measurements of Benjamin Thompson (Count Rumford) that heat could be produced by mechanical work alone. Joule produced work from falling weights suspended over pulleys attached to paddles in a thermally insulated tub of water. For a given mass of water, the same amount of work was always needed to produce a one degree rise in temperature. This was the mechanical equivalent of heat: 4.2 103 J kg1 K1 in SI units. The same value was found from dissipation of energy in a current-carrying resistor (immersion heater) for which the source of energy could also be traced back to mechanical generation with a dynamo. These experiments illustrate a general principle: If a thermally ISOLATED system is brought from one equilibrium state to another, the work necessary to achieve this change is independent of the process used. The above observation suggests that there is a state function U , the internal energy, for which U2 U1 = Wadiabatic = work done adiabatically to make the change between initial (1) and nal (2) equilibrium states. This is a restricted form of the First Law of Thermodynamics. Heat More generally, if system is not thermally isolated, W = U2 U1 (topic 03). This can be taken into account by writing U2 U1 = W + Q, where Q is the energy transfer which cannot be accounted for in terms of work, dened so that Q is positive for heat going INTO the system: Heat is the exchange of energy between the system and the surroundings that cannot be identied as work (eg mechanical work). Illustration of the dierence between W and Q In the left image below the electrical heating element is included in the system and energy is supplied as work (I.V ) whereas in the right image the heating element is outside the system and energy is supplied as heat.
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le topic04.pdf

This leads to the general statement of the First Law of Thermodynamics, for innitesimal changes: dU = d W + d Q, where both d W and d Q are path-dependent. For a compressible uid, the statement of the First Law for innitesimal reversible processes is:


system   9 e e e e e e e  I e e e e e e e

 I

gas

gas

A K e e e e e e e  e e e e e e e A 1  i P PP   A P

heating coil

system

dU = P dV + d Q

THE HEAT CAPACITY (C) OF A SYSTEM

Denition C= Heat in = lim Temperature rise T 0 Q T = dQ dT

1 Specic heat capacity is c = m C , where m is the mass of the system. Molar heat capacity often 1 also called the molar specic heat capacity is often denoted by the same symbol: c = n C, where n is the number of moles of molecules in the system.) Heat capacity at constant volume, CV

For V = constant, dV = 0 and First Law gives dUV = 0 + d QV , from which CV = d QV dUV = = dT dT U T

since U might depend on more than just temperature T . Heat capacity at constant pressure, CP The First Law now gives d QP = dUP , because V will change (dV = 0) and work is done. However, for P = constant, dHP = d(U + P V ) = dU + P dV = P dV + d QP + P dV = d QP So CP = d QP dHP = = dT dT H T

H = U + P V (with the units of energy) is called the enthalpy, and is a useful function for treatment of constant pressure processes and more generally to describe changes where the pressures of the initial and nal states are known. see later. 2

Relation between Cp and CV

Cp CV for an ideal gas From basic kinetic theory of gases, the energy of n moles of an ideal gas is equal to n 3 2 NA kB T , where NA is Avogadros constant or number and kB is Boltzmanns constant. This suggests that for an ideal gas U is a function of T only: U = U (T ). Then writing U = U (T, V ), dU dU dU = U T U = T = CV dT dT +
V

U V

dV
T

dT
V

Ideal gas only Ideal gas only

That means that dU may be replaced by CV dT in subsequent analysis for an ideal gas. Thus, using the First Law (dQ = dU + pdV ), Cp = d QP = CV + P dT V T = CV + nR
P

Ideal gas only

Cp CV for any uid Cp = H T =

P

U T

+P
P

V T

(1)
P

We want to express (U/T )P in terms of Cv = (U/T )V . Therefore use U(T,V): dU = U T U T U T U V dT +

V

U V

dV
T

=
P

+
V

V T

= Cv +
P

U V

V T

Substituting this in EQN 1 gives, Cp CV = P+ U V V T ,

P U V T

which is our nal general result. The relation for an Ideal gas can be recovered noting and calculating V T P from the ideal gas equation of state P V = nRT . The dierence comes from the work done in the constant pressure process.

=0

Constant ow processes
Consider a volume of space of any length in a constant ow process bound at its sides by stream lines and bound by two cross sections A1 and A2 perpendicular to the direction of ow at its ends (see gure). (The bounding surface along the stream lines could be the walls of a vessel). The properties of the uid are assumed constant over the cross-sections A1 and A2 (if this is not the case the areas should be taken to be suciently small for the properties to be described by a single value of the pressure over the end surfaces). The uid entering the volume element then does work P1 per unit volume of uid crossing the surface; the work is done on the uid already in the the xed volume. Per unit mass of uid entering, the the work is P1 /1 , where 1 is the density of the uid at A1 . Similarly the uid leaving extracts work per unit massP2 /2 with 2 the density of the uid leaving. The total energy/mass entering and leaving the xed volume is the sum of the kinetic energy the internal energy and the potential energy in the presence of a potential such as gravity (all per unit mass). Thus: P1 2 + 1 + gz1 1 2 2 = h1 + 1 + gz1 2 P2 2 Energy leaving at A2 = u2 + + 2 + gz2 2 2 2 = h2 + 2 + gz2 2 are the respective heights of A1 and A2 , with g the gravitational eld. Energy entering at A1 = u1 +

z1 , z2

1 , 2 are the velocities of the uid entering and leaving.

2 2 1 /2, 2 /2 are the centre of mass kinetic energies per unit mass entering and leaving.

u1 , u2 are the specic internal energy of the uid entring and leaving (ie per unit mass) h1 , h2 are the specic enthalpy of the uid. Dividing H = U + P V by mass we have h = u + P/. Because the ow process is steady, the mass enters through A1 and leaves through A2 at the same rate. Energy balance then requires that the dierence in the energy/mass is provided by any other work performed per unit mass, w (eg. viscous forces from the surrounding uid), and q , the heat transferred per unit mass to the uid in the volume element. w + q = h2 + 2 2 2 + gz2 h1 + 1 + gz1 2 2

with w and q the work done and heat transferred per mass. If there is no work done and no heat transfer (for example if the walls are adiabatic), the equation is the Bernoulli equation. If the ow is suciently fast there is also often insucient time for a signicant heat transfer, so q is negligible. If in addition no work is performed and the uid enters and leaves at the same height : 2 2 h2 + 2 = h1 + 1 2 2 The above equation has many practical uses, eg. in analysing jet engines. 4