Chapter 2

The First Law and Other Basic Concepts

Joule’s Experiments

Internal Energy

Where does the energy reside between the time that stirring work has been completed, but the heat
has not been released from the vessel, as the insulation is still there?

Internal energy is a just a concept.

Called “internal” in order to distinguish it from external forms of energy, for example (external) kinetic
and (external) potential energies.

Its symbol is 𝑈. Units are e.g. J/kg, cal/g, Specific internal energy. For molar internal energy, J/mol,
cal/lbmol etc. Total internal energy is 𝑈 𝑡 , with units only of energy.

No definition of internal energy. It is a thermodynamic primitive (‫)قدییم‬. There are no meters to measure
it.

It is distributed in so many places in the matter, that calculation of absolute values is not possible. Not
an issue here, because we need only differences.

For example, if 𝑈 of liquid water at 0oC = 0 J/kg, then if temperature is – 10oC, 𝑈 should be a negative
value. However, we know that 0oC is 273.15 degrees above absolute zero and 𝑈 cannot be 0 at 0oC. It is
only a reference value, used in calculations.
Statistical thermodynamics deals with how internal energy is distributed in matter.

The First Law of Thermodynamics (Statement not Proof)

Now we have, 𝐸𝐾 , 𝐸𝑃 , 𝑊, 𝑄, and 𝑈. in fact there are many other forms e.g. surface energy, electrical
energy, magnetic energy.

Although energy assumes many forms, the total quantity of energy is constant, and when energy
disappears in one form it appears simultaneously in other forms.

Write down three other statements of the 1st law.

The miracles of Prophets of ALLAH (SWT) do not apparently follow the laws of thermodynamics (one and
/ or all the laws). For instance, the throne of Queen Saba is presented to Hazrat Suleman (AS) before he
blinks his eyes, Hazrat Ibrahim (AS) is unaffected by the fire, Hazrat Musa (AS) shining hand is painless,
etc.

System
A region where the process occurs. The region where we are interested.

Isolated System: Neither energy, nor mass.

Closed System: Energy can, mass cannot.

Open System: Both energy and mass can.

Surroundings
Everything with which the system interacts.

Boundary
Interface of separation of system from surroundings. Itself a boundary has neither a mass nor a volume.

Real (wall), imaginary. If real, then may be rigid, moving, flexible.

According to first law, as it must include surroundings also:

∆(Energy of System)+∆(Energy of Surroundings) = 0 (1)

Energy Balance (1st Law) for Closed Systems

A closed system interacts with surroundings either through heat or through work. Therefore:

∆(Energy of Surroundings)= ±𝑄 ± 𝑊 (2)

Sign convention: Q (+ve)

W (+ve) W (-ve)

Q (-ve)
Remember sign is put with the numerical values. For example, +3 J of heat flows into the system, the
system does – 5 J of work, etc.

Put Eq (2) in Eq (1): ∆(Energy of System) ±𝑄 ± 𝑊 = 0 (3)

Now we have four “numerical” cases: +Q and +W, +Q and -W, -Q and +W, and -Q and -W. In order to
write the signs, we need to discuss only one case. The other cases are automatically settled.

For example, take the case in which both heat is added to and work is obtained by the system. Then the
“numerical” values of both are +ve:

Q = +2 J, W = +3 J, so ∆(Energy of system)= +5 J

For Eq (3) to be satisfied, then we need only – signs with both Q and W. Therefore the correct equation
is:

∆(Energy of System)−𝑄 − 𝑊 = 0

+5-(+2)-(+3)=0

∆(Energy of System)= 𝑄 + 𝑊

Often the LHS is only 𝑈 𝑡 . Then: ∆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.

(FSc Pre-engineering class use, 𝑄 − 𝑊. This is obsolete now.)

Like 𝑉 𝑡 , 𝑈 𝑡 is an extensive property. 𝑈 is an intensive property.

Extensive property depends upon the size of the system. Intensive properties are independent of the
size of the system. 𝑇 and 𝑃 are inherently intensive properties.

Axiom 1: There exists a form of energy, known as internal energy 𝑼, which is an intrinsic property of a
system, functionally related to the measurable coordinates that characterize the system. For a closed
system, not in motion, and at reference level, changes in this property are given by Eqs. (4) and (5).

Changes in 𝑈 are calculated from experimental measurements i.e. heat and work.

Vice versa, we may derive other relations from Eqs 4 and 5 that relate to directly measurable quantities
(𝑇, 𝑃 etc), and then calculate ∆𝑈 and finally 𝑄 and 𝑊 requirements.
Axiom 2: (The First Law of Thermodynamics) The total energy of any system and its surroundings is
conserved.

Conserve: total quantity does not change.

Preserve: total quantity as well as form (kind) does not change.

“Law of conservation of energy”. Energy is not preserved.

These two axioms cannot be proven, nor can they be expressed in simpler ways.

Equilibrium (absence of change)

In thermodynamics equilibrium requires that not only is system static, but also that there is no tendency
to change on macroscopic level.

All forces are in exact balance at equilibrium.

Mechanical equilibrium+ thermal equilibrium + chemical equilibrium + internal equilibrium + phase

equilibrium etc. = thermodynamic equilibrium.

A system may not be at equilibrium but still static. For example, a mixture of H2 and O2 is not in chemical
equilibrium. However, purely physical processes may be analyzed without regard to possible chemical
reaction. This is so when the system is in thermal and mechanical equilibrium.

A window glass is not in mechanical equilibrium.

A heated insulated vessel placed in air is not in thermal equilibrium.