Lecture 2

Thermodynamics

Overview:
The first law of thermodynamics talks about the conservation of energy. Energy can neither
be created nor destroyed but can be transferred/transformed from one form to another.

System: A part of the universe that is of interest. eg. An organism, a reaction vessel.
Surroundings: The rest of the universe with which the system can exchange energy.

The transfer of energy between a chemical reaction system and its surroundings can occur
in the form of work and heat.

U = q+w, where U is the change in internal energy of the system.

Work, w, is the mechanical transfer of energy from one thing to another.
Heat, q, is the energy transfer from a hot object to a cold one upon contact.

win = +ve
qin = +ve

SYSTEM
win = -ve
qin = -ve

SURROUNDINGS

Work (PV): can also be defined in terms of Pressure and volume.

Work = Force x Displacement,
and Pressure = Force/Unit area.
Force = Pressure x Area.
Hence, Work = Pressure x Area x Displacement.
 Work = Pressure x Volume. (where, Area x Displacement = Change in Volume)
Work = PV.
If system is doing work then it gives energy to the surroundings.

W = - PV.

Most biological process takes place at a constant pressure.

U = q - PV.

Heat: In any biological reaction, heat can either be released or absorbed by the system.
A reaction which absorbs heat will be endergonic in nature and a system that releases heat will be
exergonic in nature.

Enthalpy
If one observes a biological reaction taking place from the surrounding, one can
measure the amount of heat given off or absorbed during the reaction, but it is no longer equal to
the change in the internal energy of the system, because some of the heat has been converted into
work. In order to quantify the amount of heat absorbed or released during the reaction, one needs
to measure the change in enthalpy of the reaction.
Enthalpy is a quantity associated with a thermodynamic system, expressed as the internal
energy of a system plus the product of the pressure and volume of the system.
H = U + PV.
Using the relation U = q - PV,
H = (q - PV) + PV

H = q,
the heat given off or absorbed when a reaction is run at constant pressure is equal to the change in
the enthalpy of the system.

The second law of Thermodynamics:

In an isolated system, natural processes are spontaneous when they lead to an increase in
disorder, or entropy.
"Entropy" is defined as a measure of unusable energy within a closed or isolated system
(the universe for example). During a chemical reaction, as usable energy decreases and unusable
energy increases, "entropy" increases. As usable energy is irretrievably lost, disorganization,
randomness and chaos increase.