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# The 1st Law of Thermodynamics tells us that energy is neither created nor destroyed, thus the

energy of the universe is a constant. However, energy can certainly be transferred from one part of
the universe to another. To work out thermodynamic problems we will need to isolate a certain
portion of the universe, the system, from the remainder of the universe, the surroundings.
The energy transfer between different systems can be expressed as:
E1 = E2

(1)

where
E1 = initial energy
E2 = final energy

## Kelvin & Planck

"No (heat) engine whose working fluid undergoes a cycle can absorb heat from a single reservoir, deliver an
equivalent amount of work, and deliver no other effect"
Clausius
"No machine whose working fluid undergoes a cycle can absorb heat from one system, reject heat to
another system and produce no other effect"

Kelvin-Planck Statement
It is impossible to construct a heat engine which will operate continuously and convert all the heat it
draws from a reservoir into work.

OR

IT IS IMPOSSIBLE TO HEAT ENGINE WHICH WORKS IN CYCLE AND AND DOING WORK BY
EXCHANGE HEAT WITH ONLY ONE RESERVOIR.

Clausius Statement
It is impossible to construct a heat pump which will transfer heat from a low temperature reservoir to
a high temperature reservoir without using external work.
"OR"

it is impossible to flow heat from low temperature (sink) to high temperature (source) without using
expenditures.
The Third Law of Thermodynamics states that

## the entropy of any pure substance in thermodynamic equilibrium approaches zero as

the temperature approaches zero (Kelvin), or conversely

## the temperature (Kelvin) of any pure substance in thermodynamic equilibrium approaches

zero when the entropy approaches zero

## The Third Law of Thermodynamics can mathematically be expressed as

lim ST0 = 0

(1)

where
S = entropy (J/K)
T = absolute temperature (K)
At a temperature of absolute zero there is no thermal energy or heat. At a temperature of zero Kelvin
the atoms in a pure crystalline substance are aligned perfectly and do not move. There is no entropy
of mixing since the substance is pure.
The temperature of absolute zero is the reference point for determination entropy. The absolute
entropy of a substance can be calculated from measured thermodynamic properties by integrating
the differential equations of state from absolute zero. For a gas this requires integrating through
solid, liquid and gaseous phases.
The zeroth law of thermodynamics states that if two systems, A and B, are in thermal equilibrium with a
third system, C, then A and B are in thermal equilibrium with each other.