∆𝑈 𝑡 = 𝑄 + 𝑊

𝑑𝑈 𝑡 = 𝑑𝑄 + 𝑑𝑊
𝑑(𝑛𝑈) = 𝑑𝑄 + 𝑑𝑊 𝑛𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊 ∆(𝑛𝑈) = 𝑛∆𝑈 = 𝑄 + 𝑊 (4)

𝑑(𝑚𝑈) = 𝑑𝑄 + 𝑑𝑊 𝑚𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊 ∆(𝑚𝑈) = 𝑚∆𝑈 = 𝑄 + 𝑊 (5)

Division by 𝑛 or 𝑚: 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊. Upon integration: ∆𝑈 = 𝑄 + 𝑊. Units are energy/mole or

mass.

Thermodynamic State and State Functions

Internal equilibrium: When the thermodynamic properties are uniform throughout a system.

Axiom 3: The macroscopic properties of a homogeneous 𝑷𝑽𝑻 system at internal equilibrium can
be expressed as a function of its temperature, pressure, and composition.

Associated with the concept of internal equilibrium is the thermodynamic state of a system in which
the system has identifiable set of properties like 𝑇, 𝑃, 𝑉, 𝑈, and others too.

Thermodynamic properties (e.g. 𝑇, 𝑃, 𝑉, 𝑈 etc) are also called “thermodynamic state functions”.

For a “pure homogenous substance”, experience shows that fixing any two thermodynamic
properties fixes all the other values.

Homogenous: Single phase.

For example O2 gas at 300 K and 1 bar has a fixed 𝑉, 𝑈, 𝜌 etc. In fact all state functions are fixed.

Similarly, for O2 gas at 600 K and 3 bar, there are fixed values of 𝑉, 𝑈, etc: of course different from
those at 300 K and 1 bar. Now, the difference is ∆𝑉, ∆𝑈 etc. You may follow any path from state 1 to
state 2, the differences will not change.

Such properties are called state functions. They have fixed values at given temperature and
pressure, so may be represented by a graph as points in the graph. (Solve Example 2.4)

Pb

Pa

Va Vb

𝑃2 𝑉2
∫𝑃 𝑑𝑃 = ∆𝑃 ∫𝑉 𝑑𝑉 = ∆𝑉
1 1

𝑑 “infinitesimal change”, and ∆ “large change”.

On the RHS of Eqs 4 and 5 (i.e. the first law for closed systems) are the path functions. These depend
on the path of the process. These are heat and work here. For example, if you change the path you
usually follow to go for prayers to a mosque, obviously your work done by yourself on your body and
the energy released as heat, both will change.

∫ 𝑑𝑄 = 𝑄 ∫ 𝑑𝑊 = 𝑊
Here 𝑑 “infinitesimal amount”. Therefore, there is NO ∆𝑄 or ∆𝑊.

For a closed system undergoing the same change in state by several processes, experiment shows
that the amounts of heat and work required differ for different processes, but that the sum Q + W
[Eqs. 4 and 5] is the same for all processes.

Examples 2.2 and 2.3

Solve Examples 2.1 to 2.4.

Solve Problems 2.3 to 2.6, 2.12, 2.14, 2.16, 2.17.

Problem 2.3. An egg, initially at rest, is dropped onto a concrete surface and breaks. With the egg
treated as the system,

(a) What is the value of W? What is the sign of W? W=0. We are talking of PV work. No change in P,
no change in V.

(b) What is the sign of ΔEP? is -ve

(c) What is ΔEK? change in KE=0

(d) What is ΔUt? =0

(e) What is the sign of Q?

In modeling this process, assume the passage of sufficient time for the broken egg to return to its
initial temperature. What is the origin of the heat transfer of part (e)?

Solution:

∆𝐸𝑃 + ∆𝐸𝐾 + ∆𝑈 𝑡 = 𝑄 + 𝑊
You must first define state 1 and state 2. Initial state is at rest on table. EK1=0. Final state is on
ground, where the egg is again at rest. EK2=0.

The Phase Rule

Now remember our systems are at thermodynamic equilibrium.
For a pure homogenous fluid, its intensive state is fixed whenever, “any” two intensive
thermodynamic state functions are set at specific values.

In contrast, for a pure substance in two phases, we have found through experiments that only one
intensive thermodynamic state function should be fixed to define the intensive thermodynamic state
of a system. For example, a mixture of liquid water and steam at 101.325 kPa can only coexist at
100oC. Not only is the temperature fixed but the 𝑉 𝑣 and 𝑉 𝑙 , 𝑈 𝑣 , and 𝑈 𝑙 , etc. are all fixed. If only one
property is changed, for example 𝑃, all other functions will change their values and be fixed at some
new values. It also may happen by changing a single value, that one of the two phases vanishes.

Vv, Uv

T, P

Vl, Ul

For multi-phase systems, containing more than a single substance, how do we know how many
variables to be fixed, in order to define the intensive thermodynamic state of a system?

An American mathematical physicist Josiah Willard Gibbs deduced a rule in 1875, called the Gibb’s
Phase rule:

𝐹 =2−𝜋+𝑁
𝐹 = Number of degrees of freedom

𝜋 = Number of phases

𝑁 = Number of species

(Here it is written for non-reacting systems. For reacting systems, see Chapter 13. The proofs will
come in Thermodynamics 2).

(It is same rule as in Math, 𝐹 = Number of independent equations – Number of unknown variables)

The intensive thermodynamic state is fixed when 𝑇, 𝑃, and compositions of all phases are fixed. So
these are the phase rule variables.

They are not all independent, i.e., you cannot select values arbitrarily for all. How many to fix is
actually the 𝐹 value.

Phase: a homogeneous region of matter.

Continuous phases. Dispersed phases.

Abrupt changes in thermodynamic properties across the interface of two phases.

Various phases must be in equilibrium.

A boiling (vapors are also present) solution of saturated salt in water with excess solid salt. 𝜋 here is
3, N=2, so F=2-3+2=1.

Phase rule variables are intensive properties. So same answer for large or small systems, or for
different sizes of the phases.
Overall or total compositions are not phase rule variables when more than one phase is present.

Minimum value of 𝐹 = 0. So 𝜋 = 2+N. If N=1, then 𝜋=3. i.e. triple point. For water, this is 0.01oC and
0.0061 bar.

The Reversible Process

A process is reversible when its direction can be reversed at any point by an infinitesimal change
in external conditions.

Like two wrestlers pushing against each other. Or you are climbing upstairs. The slower you move,
the more reversible your work is. If you move with a lot of force, you will raise yourself highly
irreversibly.

Your parents love you, but you do not as much – irreversible.

You return that care to your parents in their old age – reversible.

Why we imagine such processes?

1) Because we want to find out the minimum amount of work required for a given change of
state in a system. We also want to find out the maximum amount of work system will
perform for a given change of state. Both are exactly same if 100% reversible. Otherwise, we
will have to do more work, or system will produce lesser work. The ratio will be called
efficiency (to be defined latter).
2) The concept is also used in derivation of thermodynamic equations because it simplifies the
derivation. However, if only state functions are involved, then such equations are equally
valid for irreversible processes too.

Reversible Expansion of a Gas

An idealized piston/cylinder arrangement imagined existing in an evacuated space. The gas trapped
inside the cylinder is chosen as the system; all else is the surroundings.

Assume that the piston slides within the cylinder without friction and that the piston and cylinder
neither absorb nor transmit heat.

Because the density of the gas in the cylinder is low and its mass is small, we ignore the effects of
gravity on the contents of the cylinder. This means that gravity-induced pressure gradients in the gas
are very small relative to its total pressure and that changes in potential energy of the gas are
negligible in comparison with the potential-energy changes of the piston assembly.

Expansion results when mass is removed from the piston.

If mass is removed suddenly, the piston rises upward quickly and initially it has maximum velocity at
the place where eventually it would come to rest. This is because the momentum carries the piston
upwards.

The piston reverses its direction and does not stop where it would finally come to rest but goes
down even further.

There are oscillations. These are dampened by the viscous nature of the gas. The viscous nature
changes the gross directed motion of molecules into a chaotic (confused) motion. This results in
energy lost as heat.
Because the forces were imbalanced from the beginning, this fact makes this process irreversible.

This dissipative process transforms some of the work initially done by the gas to raise the piston
back into internal energy of the gas.

Once the process is initiated, no infinitesimal change in external conditions can reverse its direction;
the process is irreversible.

All processes carried out in nature with finite time and real substances are irreversible in various
degrees.

Reversible processes are only imagination, but important in derivation of equations.

If the mass is replaced by a pile of powder blown very slowly from the piston. It then expands very
slowly in almost balance with the gas in the system. There are very less oscillations and only when all
the powder has blown away. So the original process approaches reversibility.

The process can be reversed if powder is replaced back slowly.

In general a process is reversible if the net force driving it is only differential in size.

For heat transfer, 𝑑𝑇; for work, 𝑑𝑃; for mass transfer 𝑑𝑐 (concentration change); for chemical
reactions chemical potential exists; for electric current flow, electromotive force exists.

Reversible Chemical Reaction

(Self Study)